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Thermodynamics 2

th
Assignment of 6
Semester

Department of Chemical
Engineering
Assignment: Thermodynamics
Barnik Goswami (Roll - 1) Deepangsu Chatterjee (Roll – 2)
1) Draw T-X-Y and P-X-Y diagram of a vapour liquid mixture.
2) What is Lewis Randell rule? State assumptions.
3) Derive modified Raoult’s law from VLE.

Solution

1)

The above figures represent the P-X-Y diagram for three temperatures (Ta, Tb, Tc) while the
T-X-Y diagram represents for three different pressures (Pa, Pb, Pc).
Dotted lines represent saturated vapour line (dew lines) while the solid lines represent
saturated liquid (vapour line).

2) The composition dependence of fugacity can be determined as –


𝜇𝑖 = 𝐾𝑖 (𝑇) + 𝑅𝑇𝑙𝑛𝑓̂̂𝑖 (1)

Similarly, 𝐺𝑖 = 𝐾𝑖 (𝑇) + 𝑅𝑇𝑙𝑛𝑓̂̂𝑖 (2)

Subtracting (2) from (1) we get


𝑓̂̂
𝜇𝑖 = 𝐺𝑖 + 𝑅𝑇𝑙𝑛 𝑓̂̂ 𝑖
𝑖

From ideal solution,


𝑓̂̂𝑖 𝑖𝑑
𝜇𝑖 𝑖𝑑 = 𝐺𝑖 𝑖𝑑 + 𝑅𝑇𝑙𝑛 𝑓̂̂𝑖
(3)

From ideal solution model,


𝑖𝑑
𝜇𝑖 𝑖𝑑 = 𝐺𝑖 = 𝐺𝑖 (𝑇, 𝑃) + 𝑅𝑇𝑙𝑛𝑓̂̂𝑖 (4)
Using (3) and (4),
𝑓̂̂𝑖 = 𝑥𝑖 𝑓̂̂𝑖 (5)

This equation is called the Lewis Randell equation, which provides the idea that fugacity of
each species in an ideal solution is proportional to the mole fraction of the species.
3)

The original Raoult’s law can be written as: 𝑦𝑖 𝑃 = 𝑥𝑖 𝑃𝑖 𝑠𝑎𝑡


Where i= 1, 2, 3…..
Now we take into account the deviation of solution ideal behaviour
𝑦𝑖 𝑃 = 𝛾𝑖 𝑥𝑖 𝑃𝑖 𝑠𝑎𝑡 (1)
Where 𝛾𝑖 = activity coefficient.
Activity coefficients are functions of temperature, pressure, liquid phase compositions and
experiments.

Using summation on both sides,


∑ 𝑦𝑖 𝑃 = ∑ 𝛾𝑖 𝑥𝑖 𝑃𝑖 𝑠𝑎𝑡 (2)
Or, 𝑃 ∑ 𝑦𝑖 = ∑ 𝛾𝑖 𝑥𝑖 𝑃𝑖 𝑠𝑎𝑡
Now, ∑ 𝑦𝑖 = 1

𝑃 = ∑ 𝛾𝑖 𝑥𝑖 𝑃𝑖 𝑠𝑎𝑡
Thermodynamics Assignment

Prantik Das (03) and Sheikh Muntazir Azam (04)

𝜕𝑙𝑛𝛾𝑖 𝑉𝑖𝐸 𝜕𝑙𝑛𝛾𝑖 −𝐻 𝐸


2.1) Prove that 𝜕𝑃
| T,Xi=
𝑅𝑇
and 𝜕𝑇
|P,Xi=
𝑅𝑇 2
, the subscript E denotes the excess property.

2.2) Why the excess property have no meaning for pure species?

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

Answers:

𝜕(𝑛𝐺 𝐸 )
Ans 2.1) We know 𝐺𝑖𝐸 = 𝜕𝑛𝑖
| 𝑇,𝑃,𝑛𝑗 as 𝐺𝑖𝐸 is a partial molar property. Using this definition we may
𝐸
𝜕(𝑛𝐺 ⁄𝑅𝑇)
identify 𝑙𝑛𝛾𝑖 to be a partial molar property as 𝑙𝑛𝛾𝑖 = 𝜕𝑛𝑖
| 𝑇,𝑃,𝑛𝑖(𝑖≠𝑗) .

As 𝑙𝑛𝛾𝑖 is a partial molar property, it must satisfy the summability relation as well as Gibbs-Duhem
𝐺𝐸 𝐺𝐸
equation . Therefore 𝑅𝑇 = ∑𝑁 𝑖 𝑁
𝑖=1 𝑥𝑖 𝑅𝑇 = ∑𝑖=1 𝑥𝑖 𝑙𝑛𝛾𝑖 (summability)

𝐺𝑖𝐸
and ∑𝑁
𝑖=1 𝑥𝑖 𝑑 = ∑𝑁
𝑖=1 𝑥𝑖 𝑑𝑙𝑛𝛾𝑖 =0 (at constant T and P).
𝑅𝑇

The fundamental excess property relation is derived in exactly the same way as the fundamental
residual property relation and leads to analogous results as follows:
𝑁
𝑛𝐺 𝐸 𝑛𝑉 𝐸 𝑛𝐻 𝐸 𝐺𝐸
𝑑 = 𝑑𝑃 − 𝑑𝑇 + ∑ 𝑑𝑛
𝑅𝑇 𝑅𝑇 𝑅𝑇 𝑅𝑇 𝑖
𝑖=1

𝑛𝐺 𝐸 𝑛𝑉 𝐸 𝑛𝐻 𝐸
=> 𝑑 = 𝑑𝑃 − 𝑑𝑇 + ∑𝑁
𝑖=1 𝑙𝑛𝛾𝑖 𝑑𝑛𝑖 . . . . . . . . . . . . (21)
𝑅𝑇 𝑅𝑇 𝑅𝑇

This is fundamental excess property relation analogous to the fundamental residual property relation.
From eq.21 we may write
𝐸 𝐸
𝜕(𝑛𝐺 ⁄𝑅𝑇) 𝑉𝑖𝐸 𝜕(𝑛𝐺 ⁄𝑅𝑇) −𝐻 𝐸
𝜕𝑃
| T, ni=
𝑅𝑇
and 𝜕𝑇
|P, ni= 𝑅𝑇 2

Once again following the definition of 𝑙𝑛𝛾𝑖 we may write ,

𝜕𝑙𝑛𝛾𝑖 𝑉𝑖𝐸 𝜕𝑙𝑛𝛾𝑖 −𝐻 𝐸


𝜕𝑃
| T,Xi=
𝑅𝑇
and 𝜕𝑇
| P,Xi=
𝑅𝑇 2

Hence Proved.

Ans 2.2) As from definition , one may formulate a different departure function called molar excess
property that quantify the deviation from ideal solution property. The mathematical formalism of
excess properties
𝑀𝐸 = 𝑀 − 𝑀𝑖𝑑

As for the pure species, it doesn’t show any deviation in an ideal solution that is why one can say that
excess property have no meaning for species.

Ans 2.3) The composition dependence of fugacity can be determined as –

𝜇𝑖 = 𝐾𝑖 (𝑇) + 𝑅𝑇𝑙𝑛𝑓̂̂𝑖 (1)

Similarly, 𝐺𝑖 = 𝐾𝑖 (𝑇) + 𝑅𝑇𝑙𝑛𝑓̂̂𝑖 (2)

Subtracting (2) from (1) we get


𝑓̂̂
𝜇𝑖 = 𝐺𝑖 + 𝑅𝑇𝑙𝑛 𝑓̂̂𝑖
𝑖

From ideal solution,


𝑓̂̂𝑖 𝑖𝑑
𝜇𝑖 𝑖𝑑 = 𝐺𝑖 𝑖𝑑 + 𝑅𝑇𝑙𝑛 𝑓̂̂𝑖
(3)

From ideal solution model,


𝑖𝑑
𝜇𝑖 𝑖𝑑 = 𝐺𝑖 = 𝐺𝑖 (𝑇, 𝑃) + 𝑅𝑇𝑙𝑛𝑓̂̂𝑖 (4)
Using (3) and (4),
𝑓̂̂𝑖 = 𝑥𝑖 𝑓̂̂𝑖
(5)

This equation is called the Lewis Randell equation, which provides the idea that fugacity of
each species in an ideal solution is proportional to the mole fraction of the species.
Assumptions of these rule are:
1) Valid for simple solution, for the entire non-simple solution Lewis-Randall is valid.
2) Invalid for simple solution at infinite dilution.

The plot of 𝑓̂̂𝑖 𝑣𝑠 𝑥𝑖 is given below:


THERMODYNAMICS ASSIGNMENT

SUBMITTED BY – SREEJITA BANERJEE (ROLL- 19), AYAN KANTI SANTRA (ROLL- 27)

B.TECH 6 TH SEMESTER

QUESTION: 1. Prove that for a first order phase transition for an ideal gas ---

𝑑𝑙𝑛𝑝 (𝑠𝑎𝑡 ) −∆𝐻


1 =
𝑑( ) 𝑅
𝑇

Answer : For a first order phase transition from phase 1 to phase 2 we have,

G1 = G2
dG1 = dG2
-S1dT+V1dP(sat)= -S2dT + V2 dP(sat)
𝑑𝑃(𝑠𝑎𝑡 ) ∆𝑆
= ∆𝑉
𝑑𝑇
∆𝐻
AGAIN , 𝑇 = ∆𝑆
𝑑𝑃(𝑠𝑎𝑡 ) ∆𝐻
THEREFORE, 𝑑𝑇
= 𝑇∆𝑉
Considering simple liquid to vapour transition , we have some assumptions..
1) ∆H to be indepndent of temperature.
2) Vapour phase is assumed to behave ideally.
3) VV >> VL , So ∆V = VV-VL = VV
With these assumptions the desired equation becomes ,
𝑑𝑃 (𝑠𝑎𝑡) ∆𝐻× 𝑃(𝑠𝑎𝑡 )
= 𝑇× 𝑅𝑇
𝑑𝑇
𝑑𝑃(𝑠𝑎𝑡 ) 1 ∆𝐻
Or, 𝑃(𝑠𝑎𝑡 ) × 𝑑𝑇 = 𝑅
2 𝑇
𝑑𝑙𝑛 𝑃(𝑠𝑎𝑡 ) ∆𝐻
Therefore, 1 = − (PROVED)
𝑑( ) 𝑅
𝑇

QUESTION 2 : An equimolar liquid mixture of species 1 and species 2 is in equilibrium with its vapor
phase at 400K. At this temperature vapor pressure o species 1 and 2are P1(sat) 180 kpa and P2(sat)
120 kpa. Assuming Raoults law is valid calculate y1 and y2.
ANSWER: As given in problem, for equimolar liquid mixture we get, x1=x2=0.5
Therefore, Total Pressure P = x1×P1(sat) +x2×P2(sat)
= 0.5× 180 + 0.5 × 120
= 90 + 60
= 150
𝑃1 𝑥1 ×𝑃1(𝑠𝑎𝑡 ) 0.5×180
Therefore , y1 = = = = 0.6
𝑃 𝑃 150
y2 = (1-0.6) = 0.4
Therefore, vapor composition of species 1 = 0.6
And, vapor composition of species 2 = 0.4
QUESTION 3 : Prove that : GiR/RT = ln øi = ʃ0p (zi-1) dP/P
Ans: For a pure species ideal gas we have ,

dGig = ViigdP , (at constant temperature)

Vig = RT/P ,

Hence, dGig = RT dlnP or Giig=RTlnP+⌠i(T)

Now for a real gas, we can deduce similarly,

dGiig = RTdlnfi ( fi=fugacity of pure species),

Now dGiR=RTdln(fi/p) (dGiR=dGi-dGiig) Where, øi=fugacity co-eff of species i=fi/p

Hence dGiR =RT(dlnøi) (at constant temp)

Integrating , GiR/RT = lnøi+Ci(T)

Now at constant temp GiR/RT =lnøi

We know that for ideal gas dGiig=ViigdP

And for real gas dGi=VidP

Hence dGi-dGiig=(Vi-Viig)dP

Or, dGiR=ViRdP

We know that, Vi=ZiRT/P for real gases, where Zi=compressibility factor.

ViR=(ZiRT/P)-(RT/P)

= RT(Zi-1) /P

Therefore, dGiR= RT(Zi-1) dP/P

Integrating , GiR/RT = ʃ0P (Zi-1) dP/P (at constant temp)

Hence , lnøi= GiR/RT = ʃ0P (Zi-1)dP/P (PROVED)

QUESTION : 4 The Van Laar Constants A and B for the system Nitro-methane (1) and CCl4 (2) at
45◦C are 2.230 and 1.959 respectively. Calculate activity coefficients of component in a solution
containing 30 mole percent Nitro-methane ?

Ans : From the Van Laar model we have, ln ⌠1 = A/(1+ (Ax1/Bx2))2

= 2.23÷ (1+ (2.23×.3)/(1.959×.7))2

= 1.00735

⌠1 = 2.7385

Again similarly we have , ln ⌠2 = B/(1+(Bx2÷Ax1))2 = 1.959/(1+(1.959×.7/2.230×.3))2

Or, ⌠2=1.2344

Here A and B are the Van Leer constants for species 1 and 2

And ⌠1 and ⌠2 are the activity coefficients of species 1 and 2 respectively.


Assignment solution
Name : anuj Debnath(42) , Monami Mitra (25)

Q1. State Duhem’s theorem?


Q2. What are the assumptions required to reduce VLE calculation?
Q3. For the system methanol (1) methyl acetate (2), the following equations provide a
reasonable correlation for the activity coefficients

𝑙𝑛𝛾1 = 𝐴𝑥22 , 𝑙𝑛𝛾2 = 𝐴𝑥12 where A = 2.771 – 0.00523T 𝑙𝑛𝑃1𝑠𝑎𝑡 = 16.59158 −


3643.31 2665.54
, 𝑙𝑛𝑃2𝑠𝑎𝑡 = 14.25326 −
𝑇−33.424 𝑇−53.424

i. Determine P and (𝑦𝑖 ) for T = 318.15 and 𝑥1 = 0.25


ii. Determine P and (𝑥𝑖 ) for T = 318.15 and 𝑦1 = 0.60 (assume modified
Roult’s Law)
iii. Determine T and 𝑦𝑖 for P = 101.33 KPa and 𝑥1 = 0.85
Q4. What is the vapour pressure of 40% gas in a system with partial pressure 20mmHg?

Ans 1: The Gibbs –Duhem theorem equation describes the relationship between changes in
chemical potential of compon
ents in a thermodynamic system.
𝑉𝑑𝑝 − 𝑆𝑑𝑝 = ∑𝑛𝑖=1 𝑁𝑖𝜇𝑖 (for a closed system)
Ni = number of moles of component i

Duhem’s theorem is stated as follows: for any closed system formed initially from given
masses of prescribed chemical species, the equilibrium state is completely determined
when any two independent variables are fixed.
Ans 2: the two major assumption required to reduce VLE calculation to Roults Law are –
a. The vapour phase is an ideal gas.
b. The liquid phase is an ideal solution .

Ans 3 : A buble p calculation:


The Antoin equation yield - T=318.15K (given)
A=2.771-0.00523T
=2.771-0.00523*318.15
=1.1070755

ln𝛾1 = 𝐴𝑥22 𝑙𝑛𝛾2 = 𝐴𝑥12


𝑥2 = 1 − 𝑥1 = 1 − 0.25 = 0.75; 𝑥1 = 0.25 (𝑔𝑖𝑣𝑒𝑛)
𝑙𝑛𝛾1 = 1.1070755 ∗ 0.752 𝑙𝑛𝛾2 = 1.1070756 ∗ 0.252
𝑜𝑟, 𝛾1 = 1.864 𝛾2 = 1.0716

From Antoin eqn ,


3643.31
𝑙𝑛𝑃1𝑠𝑎𝑡 = 16.59158 − 𝑇−33.424 𝑇 = 318.15 (𝑔𝑖𝑣𝑒𝑛)
or, 𝑃1𝑠𝑎𝑡 = 44.5 𝐾𝑃𝑎
2665.54
Similarly, 𝑙𝑛𝑃2𝑠𝑎𝑡 = 14.25326 − T=318.15(given)
𝑇−53.424
or 𝑃2𝑠𝑎𝑡 = 65.64 𝐾𝑃𝑎
For a binary system,

𝑃 = 𝑥1 𝛾1 𝑃1𝑠𝑎𝑡 + 𝑥2 𝛾2 𝑃2𝑠𝑎𝑡
P= 0.25*1.86*44.5 + 0.75*1.07*65.64
P = 73.50
From modified Roults Law

𝑦𝑖 𝑃 = 𝑥𝑖 𝛾𝑖 𝑃𝑖𝑠𝑎𝑡
𝑥1 𝛾1 𝑃1𝑠𝑎𝑡
𝑦1 = 𝑃

= (.25*1.864*44.5)/73.50
= 0.282
Similarly, y2 =0.718
b) dew P calculation :
T = 318.15K
Hence, A = 1.107055
𝑦1 = 0.60 , (given) 𝑦2 = 1 − 0.60 = 0.40

𝑃1𝑠𝑎𝑡 = 44𝐾𝑃𝑎 𝑎𝑛𝑑 𝑃2𝑠𝑎𝑡 = 65.64 𝐾𝑃𝑎


Here liuid-phase composition are unknown, but are required for the calculation of activity
co-efficients. We have to follow an iterative procedure. Initial values are provided by Roults
Law (𝛾1 = 𝛾2 = 1.0 for ideal solution)

For binary solution


P = 1/(𝑦1 /𝛾1 𝑝1𝑠𝑎𝑡 + 𝑦2 /𝛾2 𝑝2𝑠𝑎𝑡 ) = 1/(0.60/1*44.5 +0.40/1*65064) = 51.080
𝑦1𝑃
𝑥1 = 𝛾1𝑃𝑠𝑎𝑡 =( 0.60*51080)/(1*44.5) = 0.6887
1

𝑦2 𝑃
Similarly x2 = 𝛾 𝑠𝑎𝑡 = 0.311
2 𝑃2
𝑙𝑛𝛾1 = 1.1070755 ∗ 0.752 𝑙𝑛𝛾2 = 1.1070756 ∗ 0.68872 𝛾1 =
1.113 𝛾2 = 1.6906
Iteration
P X1 X2 𝛾1 𝛾2

1 51.080 0.6887 0.311 1.113 1.6906


2 63.040 0.76 0.236 1.0636 1.895
3 62.92 0.7976 0.202 1.046 2.022
4 62.877 0.81049 0.1895 1.04056 2.069
5 62.88 0.81479 0.185 1.0387 2.085
6 62.87 0.8162 0.1837 1.038 2.0907
7 62.876 0.816 0.183 1.0378 2.089
8 62.83 0.816 0.183 1.038 2.089

We find , P= 62.8KPa X1=0.816 X2= 0.183 𝛾1 = 1.038 𝛾2 = 2.09

C).Bubble T and yi calculation ( given P =101.33KPa Xi= 0.85)

Pi sat are needed for calculation but T is unknown. Hence iterative procedure adopted. For
the purpose of finding an initial temperature to start on iteration, we need values of
saturation temp. of pure species 𝑇𝑖𝑠𝑎𝑡 at pressure P= 1010.33KPa
3643.31
From the given eqn we can write 𝑇1𝑠𝑎𝑡 = 16.59158−𝑙𝑛(101.33) + 33.424 = 337.712
..eq1

And 𝑇2𝑠𝑎𝑡 = 2665.56/(14.25326-ln(101.33)) +53.424 = 330.0793

Therefore Told =∑ 𝑥𝑖 𝑇𝑠𝑎𝑡 𝑠𝑎𝑡 𝑠𝑎𝑡


𝑖 = 𝑇1 𝑥1 + 𝑥2 𝑇2

Or, Told = 336.5678

For initial estimate we set T = Told = 336.5678, putting this T in eqsn


3643.31 2665.54
𝑙𝑛𝑃1𝑠𝑎𝑡 = 16.59158 − 𝑇−33.424 𝑙𝑛𝑃2𝑠𝑎𝑡 = 14.25326 − 𝑇−53.424
𝑠𝑎𝑡 𝑠𝑎𝑡
We get 𝑃1𝑜𝑙𝑑 = 96.84945239 𝑃2𝑜𝑙𝑑 = 126.3649002
𝑃𝑠𝑎𝑡
Now, 𝑃1𝑠𝑎𝑡 1𝑜𝑙𝑑
𝑛𝑒𝑤 = 𝑝/(𝑥1 𝛾1 + 𝑥2 𝛾2 (𝑃𝑠𝑎𝑡 ) )
2𝑜𝑙𝑑

Given- A= 2.771-0.00523T and putting T= 336.5678 we get A = 1.01075 and putting A in


the following eqns 𝑙𝑛𝛾1 = 𝐴𝑥22 , 𝑙𝑛𝛾2 = 𝐴𝑥12
We find 𝛾1 = 1.023002 𝑎𝑛𝑑 𝛾2 = 2.075635

Now 𝑃1𝑠𝑎𝑡
𝑛𝑒𝑤 = 79.42581419

Putting this 𝑃1𝑠𝑎𝑡


𝑛𝑒𝑤 in eq1 we can find T1 new

T1new = 3643.31/(16.59158-ln𝑃1𝑠𝑎𝑡
𝑛𝑒𝑤 ) + 33.424 = 331.6464

Similarly for other iteration

𝑠𝑎𝑡 𝑠𝑎𝑡
Told A 𝛾1 𝛾2 𝑃1𝑜𝑙𝑑 𝑃2𝑜𝑙𝑑 𝑃1𝑠𝑎𝑡
𝑛𝑒𝑤
T new
2. 331.6464 1.03649 1.02359 2.11459 79.425814 106.980844 78.109160
331.2389
3. 331.2389 1.03862 1.023644 2.11785 78.109160 105.487978 77.998459
331.2043
4. 331.2043 1.03880 1.023648 2.11813 77.998459 105.36226 77.989069
331.2014

5. 331.2014 1.03881 1.023649 2.11815 77.898069 105.35160 77.988272


331.2012
Therefore iteration to convergence on a value for T yields final values:
T=331.20 K(Ans) 𝑃1𝑠𝑎𝑡 =77.89Kpa 𝑃2𝑠𝑎𝑡 =105.35KPa
A=1.3088 𝛾1=1.0236 𝛾2=2.1182
The vapor-phase mole fractions are given by;
𝑥1 𝛾1 𝑝1𝑠𝑎𝑡
𝑦1 = =0.67(Ans)
𝑃

And y2 = (1-y1) =(1-0.67) = 0.33 (Ans)


THERMODYNAMICS ASSIGNMENT (B.TECH CHEMICAL ENGINEERING 6TH SEMESTER)

SUBMITTED BY:- MOUMITA MAITY ROLL-29

AMRITA DEBNATH ROLL-14

1.a)Prove that change of entropy increases for ideal gas mixing.

1.b)A chamber with a partition contains 0.1 Ib-mole of N2 and 0.1 Ib-mole of O2 at 70 degree F & 1
atm. The partition is removed and gasses allowed to mix. Calculate the total change of entropy of the
system due to mixing.

1.c) Ethanol(1)/Benzene(2) system forms an azeotrope with 44.8%(mole) of ethanol with a boiling
point of 68.24 degree C at 760 torr. The vapour pressure of ethanol and benzene at 68.24 degree C
are 506 torr and 517 torr. Estimate the Van-laar constant for the system and evaluate the activity
coefficients for a solution containing 10% (mole) ethanol.

Ans:-

1.a) dsi ig= CPig (dT/T)-RdlnP


pure 𝑃
at constant temp., ∫mix dSi ig=-∫Pi RdlnP
Siig(T,Pi)-Siig(T,P)=-Rln(Pi /P)=-Rln(yiP/P)=-Rlnyi
Siig (T,Pi)= Siig (T,P)-Rlnyi ………………………………(1)
From Gibb’s theorem, fi̅ ig(T,P)=fiig (T,Pi)
So, S̅iig (T,P)= Siig (T,Pi)
From equation (1)
S̅iig(T,P)= Siig (T,P)-Rlnyi…………………(2)

S̅iig= Siig -Rlnyi

Sig=Σyi S̅iig = ΣyiSiig -RΣyilnyi


Sig= ΣyiSiig -RΣyilnyi…………………………………..(3)

ΔSmixing= -RΣyilnyi

y i<1, So, ΔSmixing>0


So, change of entropy increases for ideal mixing (proved)

1.b) ΔS=-RΣyi lnyi


ΔS=-R [0.5ln0.5+0.5ln0.5]=-Rln0.5 Btu/(mole.R)
[since yi=(0.1/0.2)=0.5 ]
Total change in entropy:-
=-0.2Rln0.5
=0.2×1.987×ln2
=0.274 Btu/R

1.c) yi P = γi xi Pis
At azeotropic point ,yi=xi
So,P= γi PIS
γi =P/ Pis
γ1=760/506=1.502 ; γ2=760/517=1.470
A=ln1.502[1+ (0.552ln1.470/0.448ln1.502)]2= 1.910
B=ln1.470[1+(0.448ln1.502/0.552ln1.470)]2= 1.3285
At x1=0.10
lnγ1= 1.910/[1+(1.910×0.10)/(1.3285×0.90)]2= 1.420
γ1=4.317

lnγ2=1.3285/[1+(1.3285×0.90)/(1.910×0.10)]2=0.0252
γ2=1.0255
Assignment On Thermodynamics
Compiled by:
TOUSIF JAMAL, ROLL: 034
PRIYA SINGH, ROLL: 035

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

Given, Antoine’s constants----

components Ai Bi Ci
n-pentane(1) 6.87632 1075.78 233.205
n-heptane(2) 6.89386 1264.37 216.640

2: Draw T-x-y and P-x-y diagram of a VLE.

Solution:

Given pressure P= 600torr

x1= 0.4 (i.e., the mole fraction of n-pentane in liquid phase)

the bubble point temperature of the solution is to be determined.

Antoine’s equation is given by,


𝐵
ln 𝑝𝑖𝑠𝑎𝑡 = 𝐴𝑖 − 𝐶 +𝑇
𝑖
--------------1(a)
𝑖

𝐵𝑖
 𝑇= − 𝐶𝑖 ------------1(b)
𝐴𝑖 −𝑙𝑛𝑝𝑖𝑠𝑎𝑡

For purpose of finding an initial temperature to start an iteration procedure we need values of
saturation temperature of the pure species i.e., 𝑇𝑖𝑠𝑎𝑡 at pressure P=600 torr. These are also given by
Antoine equation as,
𝐵𝑖
𝑇𝑖𝑠𝑎𝑡 = − 𝐶𝑖 --------------------(2)
𝐴𝑖 −𝑙𝑛𝑃

Now, for n-pentane(1),


𝐵1
𝑇1𝑠𝑎𝑡 = − 𝐶1
𝐴1 − 𝑙𝑛𝑃
1075.78
 𝑇1𝑠𝑎𝑡 = 6.87632−ln(600) − 233.205

 𝑇1𝑠𝑎𝑡 = 2010.854

And for n-heptane(2),


𝐵2
𝑇2𝑠𝑎𝑡 = 𝐴 −𝑙𝑛𝑃
− 𝐶2
2

1264.37
 𝑇2𝑠𝑎𝑡 = 6.89386−𝑙𝑛(600) − 216.640

 𝑇2𝑠𝑎𝑡 = 2327.721

For an initial estimate, we set our guess value

𝑇 = ∑ 𝑥𝑖 𝑇𝑖𝑠𝑎𝑡

 𝑇𝑜𝑙𝑑 = 𝑥1 𝑇1𝑠𝑎𝑡 + 𝑥2 𝑇2𝑠𝑎𝑡 where x2= (1-x1)


 𝑇𝑜𝑙𝑑 = 0.4 × 2010.854 + 0.6 × 2327.721
 𝑇𝑜𝑙𝑑 = 2200.974

Putting Told in eqn-(1a), we get

𝑠𝑎𝑡 1075.78
𝑙𝑛𝑝1(𝑜𝑙𝑑) = 6.87632 −
233.205 + 2200.974
𝑠𝑎𝑡
 𝑝1(𝑜𝑙𝑑) = 622.891

And,
𝑠𝑎𝑡 1264.37
𝑙𝑛𝑝2(𝑜𝑙𝑑) = 6.89386 −
216.640 + 2200.974
𝑠𝑎𝑡
 𝑝2(𝑜𝑙𝑑) = 584.570

We know for a binary system

𝑃 = 𝑥1 𝛾1 𝑝1𝑠𝑎𝑡 + 𝑥2 𝛾2 𝑝2𝑠𝑎𝑡

𝑃
 𝑝1𝑠𝑎𝑡 = 𝑝𝑠𝑎𝑡 --------------------(3)
𝑥1 𝛾1 +𝑥2 𝛾2 ( 2𝑠𝑎𝑡 )
𝑝1

Assuming the solution to be ideal, we put 𝛾1 = 𝛾2 = 1

Therefore from eqn-(3),

𝑠𝑎𝑡 𝑃
𝑝1(𝑛𝑒𝑤) = 𝑠𝑎𝑡
𝑝2(𝑜𝑙𝑑)
𝑥1 + 𝑥2 ( 𝑠𝑎𝑡 )
𝑝1(𝑜𝑙𝑑)

𝑠𝑎𝑡 600
 𝑝1(𝑛𝑒𝑤) = 584.570
0.4+0.6×( )
622.891

𝑠𝑎𝑡
 𝑝1(𝑛𝑒𝑤) = 622.996

𝑠𝑎𝑡 1
Putting the value of 𝑝1(𝑛𝑒𝑤) in eqn-(1b) to get 𝑇𝑛𝑒𝑤

1 𝐵1
Therefore, 𝑇𝑛𝑒𝑤 =𝐴 𝑠𝑎𝑡 − 𝐶1
1 −𝑙𝑛𝑝1(𝑛𝑒𝑤)
1 1075.78
 𝑇𝑛𝑒𝑤 = 6.87632−ln(622.996) − 233.205
(1)
 𝑇𝑛𝑒𝑤 = 2201.903 ℃

1
For second iteration we set our guess value Told = 𝑇𝑛𝑒𝑤 = 2201.903℃ and proceed in a similar way, we
obtain,

𝑠𝑎𝑡
𝑝1(𝑜𝑙𝑑) = 622.996

𝑠𝑎𝑡
𝑝2(𝑜𝑙𝑑) =584.688

𝑠𝑎𝑡
𝑝1(𝑛𝑒𝑤) =622.984

(2)
And hence, 𝑇𝑛𝑒𝑤 =2201.798 ℃

(setting Told = 2201.798℃ )

𝑠𝑎𝑡
𝑝1(𝑜𝑙𝑑) = 622.985

𝑠𝑎𝑡
𝑝2(𝑜𝑙𝑑) =584.675

𝑠𝑎𝑡
𝑝1(𝑛𝑒𝑤) =622.986

(3)
And hence, 𝑇𝑛𝑒𝑤 =2201.810 ℃

Iteration-4 (Told = 2201.810 ℃ )

𝑠𝑎𝑡
𝑝1(𝑜𝑙𝑑) = 622.986

𝑠𝑎𝑡
𝑝2(𝑜𝑙𝑑) =584.676

𝑠𝑎𝑡
𝑝1(𝑛𝑒𝑤) =622.986

(4)
And hence, 𝑇𝑛𝑒𝑤 =2201.809 ℃

Iteration-5: (Told = 2201.809℃)

𝑠𝑎𝑡
𝑝1(𝑜𝑙𝑑) =622.986

𝑠𝑎𝑡
𝑝2(𝑜𝑙𝑑) =584.676

𝑠𝑎𝑡
𝑝1(𝑛𝑒𝑤) =622.986

(5) (4)
And hence, 𝑇𝑛𝑒𝑤 =2201.809 ℃ = 𝑇𝑛𝑒𝑤

So the temperature converges at T = 2201.809


Therefore, the bubble point of the solution of n-pentane/n-heptane with the given condition is
2201.809℃ (Ans)

2: T-x-y and P-x-y diagram of VLE

T-x-y diagram

Consider a binary solution of benzene and toluene. Let the mole fraction of benzene in vapour phase
be y1 and in liquid phase be x1. Since benzene is more volatile, y1>x1. At constant pressure, we may
represent the VLE data in terms of T-x-y diagram as shown:

The adjuscent diagram consist of three


regions:

(i) Sub-cooled liquid (L)


(ii) Vapour – liquid mixture (V+L)
(iii) Super heated vapour (V)

Consider a vertical line of overall


composition z1. At point 1, vapour phase
exists.

As the system is cooled, a temperature


comes when it touches the two phase
region and the first drop of liquid is formed.
This is known as Dew Point. (point-2),
which is shifted to get Dew point curve.

When further cooled, liquid and vapour


both the phases exist. The composition of
Fig-1: T-x-y diagram which can be obtained by drawing a
horizontal tie line at the definite temperature.

On further reduction of temperature, point-3 is reached, when the last amount of vapour is converted
into liquid. The corresponding location is called Bubble Point., which can be shifted to obtain the Bubble
point curve.

On further reduction beyond point-3, we reach in the liquid phase region which is the Sub-cooled
liquid(L). (at point-4).
P-x-y Diagram

consider a system consisting of two components of which the first one is more volatile i.e., y 1>x1 and
𝑝1𝑠𝑎𝑡 > 𝑝2𝑠𝑎𝑡 .

In the adjuscent diagram we have three regions:

(i) Sub-cooled liquid (L)


(ii) Vapour – liquid mixture (V+L)
(iii) Super heated vapour (V)

Consider a vertical line of overall composition


z1. At point 1, super-cooled liquid exists. On
reduction of pressure, till point-2, a stage
comes when the first bubble of vapour forms,
called the bubble point and the corresponding
pressure is called Bubble point pressure.

On further reduction of pressure , a two phase


region is reached, the composition of which Fig-2: P-x-y diagram

can be calculated with the help of a tie line as


shown at point 3. If we still go on reducing the pressure, the stage come when whole liquid is converted
to vapour phase(at point-4), called Dew point and the corresponding pressure is called the Dew point
pressure. Point-4 is followed by super heated vapour at point-5 obtained by further reduction in
pressure.
THERMODYNAMICS ASSIGNMENT
BY- ABHISHEK KUNDU (ROLL NO-38) & SOHRAB KHAN (ROLL NO-15)
Q1.Define simple and non-simple solution.

Ans: Simple solutions are also known as ideal solution. These are the solutions or mixture that obeys
Roult’s law if it is a mixture of liquid in which equilibrium exists between liquid and vapour. But the
solution of liquid which obeys Lewis Randall rule or Lewis fugacity rule it states that fugacity of a
component in an ideal solution is directly proportional to mole fraction of component in the solution.

Non simple solution are also called real solution. These are the solution which deviates from
ideality.An activity coefficient (yi) is a factor used in thermodynamics to account for deviation from
ideal behaviour in a mixture of chemical substance.

yi=(f^i)/(f°I × ui )

Q2.Graphically depict variation of y1 and y2 vs mole fraction for two suffix Margule’s model.

Ans:

Q3.The van Laar activity coefficient model for a binary mixture is given by the form

lnɣ1=A*/ {1+ (A*x1/B*x2)} 2; lnɣ2=B*/ {1+ (B*x2/A*x1)} 2

Given, ɣ1 = 1.40; ɣ2 =1.25; x1 =0.25; x2 =0.75, determine the constants B* & A*.

Ans: lnɣ1=A*/ {1+ (A*x1/B*x2)} 2

Putting the values of ɣ1 = 1.40; x1 =0.25; x2 =0.75, we got

ln (1.40)=A*/ [1+ {A*(0.25)/B*(0.75)}] 2

or,0.336= A*/ [1+ {A*(0.25)/B*(0.75)}] 2 ……………..eq(1)

Also lnɣ2=B*/ {1+ (B*x2/A*x1)} 2

Putting values of ɣ2= 1.25; x1 =0.25; x2 =0.75, we got


ln (1.25)=B*/ [1+ {B*(0.75)/A*(0.25)}] 2

or ,0.223 = B*/ [1+ 3 B*/ A*]2 …………………………………eq(2)

Expanding eq(1) we get

0.0365 (A*/B*)2 +0.221( A*/B* )+(0.336- A*)=0

Let (A*/B*) = β

So,0.0365 β2+0.221β+(0.336- A*)=0…………………………………….eq(3)

Expanding eq(2) we get

0.223 = B*/ [1+ 9(B*/A*)2+6(B*/A*)]

So,2.007 β2+1.338β(0.223-B*)=0………………………………………….eq(4)

Now we have two equation and two variables A* and B*

From eq(3) by applying Sridharacharya

β= [(-0.221) ± {(0.221)2-4(0.0365) (0.336- A*)} (0.5)] / (2×0.0365)

β= [(-0.221) ± {0.0488-0.146(0.336- A*)} (0.5)] / (0.073)………….eq(5)

From eq (4) by applying Sridharacharya

β= [(-1.338) ± {(1.338)2- 4(2.007) (0.223 - B*)} (0.5)]/ (2×2.007)

β = [(-1.338) ± {1.7902-8.028(0.223- B*)} (0.5)]/ (4.017)………….eq (6)

from eq (5) & eq (6) we get following equation

[(-0.221) ± {0.0488 - 0.146(0.336 - A*)} (0.5)] / (0.073) = [(-1.338) ± {1.7902- 8.028(0.223 - B*)} (0.5)] /
(4.017)

Or, (-0.887) + 4.014{0.0488- 0.146(0.336-A*)} (0.5) = (-0.097) + 0.073{1.7902- 8.028(0.223-B*) (0.5)


Or, 0.0221+ 0.0488A*- 2.601B* + 0.007056 {1.7902 – 8.028(0.223 – B*)} (0.5) = 0

By solving this equation and substituting in eq(3) and eq(4) we get that

A*=0.336

B* =0.223
ASSIGNMENT: THERMODYNAMICS-2
NAME: SAYANI RAKSHIT, ROLL-041
MAHARGHYA BISWAS, ROLL-024

1.a. Derive Henry’s law from Lewis Randall Rule.

b. A methanol-water vapor liquid system is at equilibrium at 60◦ C & 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 60◦ C are 85 KPa &
20 KPa respectively. Assume vapor pressure to be an ideal gas mixture.

i. What is the activity co-efficient of water liquid mixture in liquid phase?

ii. What is the excess Gibb’s free energy (𝒈𝑬 𝒊𝒏 𝑱/𝒎𝒐𝒍) of liquid mixture?

SOLUTION:

1.a. For an ideal solution 𝑓̂̂̂𝑖𝑑 0


𝑖 = 𝑓̂̂𝑖 𝑥𝑖 .

For simple solution we may write 𝑓̂̂𝑖0=𝑓̂̂𝑖 and the resulting equation becomes

𝑓̂̂̂𝑖𝑑
𝑖 = 𝑓̂̂𝑖 𝑥𝑖 ………………..<1>

The above equation is known as Lewis-Randell rule, applies to each species in an ideal solution at all
condition of temperature, pressure & composition.

It shows that fugacity of each component in an ideal solution is proportional to its mole fraction &
the proportionality constant is the fugacity of pure component (1) in the same physical state as the
solution at same temperature and pressure.

However, for entire non-simple solution group, L-R rule is invalid & the very definition of standard
state becomes fictitious. Even for simple solution at infinite dilution L-R rule is not valid. In order to
solve the problem, let us consider a simple solution at infinite dilution ( 𝐿𝑒𝑡, 𝑥𝑖 → 0 ) .
̂
At, 𝑥𝑖 = 0, 𝑓̂̂𝑖𝑖𝑑 →0
𝑓̂̂̂
Therefore, ration of 𝑥𝑖 is indeterminate in this time and application of L’ Hospital’s rule yields,
𝑖

𝑓̂̂̂
𝑖
𝑖𝑑 𝑑 𝑓̂̂̂
𝑖
𝑖𝑑
lim = ………………..<2>
𝑥𝑖 →0 𝑥𝑖 𝑑𝑥𝑖

Derivation of slope of 𝑓̂̂̂𝑖𝑑


𝑖 vs 𝑥𝑖 curve at 𝑥𝑖 = 0 is defined as a species-specific constant, 𝑘𝑖 .
Therefore,

𝑓̂̂̂
𝑖
𝑖𝑑 𝑑 𝑓̂̂̂
𝑖
𝑖𝑑
lim = ≡ 𝑘𝑖 ………………..<3>
𝑥𝑖 →0 𝑥𝑖 𝑑𝑥𝑖

By introducing a species-specific constant, we get rid of the fictitious standard state property ( 𝑓̂̂𝑖0).

Hence, for simple solution, at infinite dilution & for the entire spectrum of non-simple solution, we
may write,
𝑓̂̂̂𝑖𝑑
𝑖 = 𝑘𝑖 𝑥𝑖 ………………..<4>

Where, 𝑘𝑖 ≡ Henry’s Law constant and equation <4> is Henry’s Law.

1.b. (1) (2)

MeOH-H2O system

𝑥1 = 0.5 mole fraction of CH3OH in liquid Phase

𝑦1 = 0.8 mole fraction of CH3OH in vapor phase.

𝑥2 = 0.5 mole fraction of H2O in liquid phase

𝑦2 = 0.2 mole fraction of H2O in vapor phase. T = 60◦ C


𝑣𝑎𝑝
𝑝𝐴 = 85 kPa, vapor pressure of CH3OH P = 60 kPa
𝑣𝑎𝑝
𝑝𝐵 = 20 kPa, vapor pressure of H2O

Now,
𝑣𝑎𝑝 Where 𝛾2 = activity co-efficient of water in liquid phase
𝑦2 𝑝 = 𝑥2 𝛾2 𝑝𝐵

0.2 × 60 = 0.5 × 𝛾2 × 20
∴ 𝛾2 = 1.2
The activity co-efficient of water in liquid phase is 1.2.

We know,

𝑔𝐸 = 𝑅𝑇[𝑥1 ln 𝛾1 + 𝑥2 ln 𝛾2 ] (𝑔𝐸 = 𝐸𝑥𝑐𝑒𝑠𝑠 𝐺𝑖𝑏𝑏𝑠 𝑓̂̂𝑟𝑒𝑒 𝑒𝑛𝑒𝑟𝑔𝑦)


Again,
𝑣𝑎𝑝
𝑦1 𝑝 = 𝑥1 𝛾1 𝑝𝐴

60 × 0.5 = 0.5 × 𝛾1 × 8.5


60 × 0.8
∴ 𝛾1 =
0.5 × 8.5
=1.129

∴ 𝑔𝐸 = 8.314 𝐽 𝑚𝑜𝑙 −1 𝑘 −1 × (273 + 60)𝐾 × [0.5 ln 1.129 + 0.5 ln 1.2 ]


(2.768.56 × 0.1518) 𝐽𝑚𝑜𝑙 −1

= 420.34 𝐽𝑚𝑜𝑙 −1
Therefore, the excess Gibbs free energy in liquid mixture is 420.34 𝐽𝑚𝑜𝑙 −1.
Name : Amarendra Sinha(20), Amit Das(22)

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

H=400x1 +600x2+x1x2(40x1+20x2)

Where H is in J/mol.Determine ̅̅̅̅


𝑯𝟏 and ̅̅̅̅
𝑯𝟐 as functions of x1, numerical values for pure species
̅̅̅̅̅̅̅ and
enthalpies(H1 and H2) and numerical values for the partial enthalpies at infinite dilution(𝑯𝟏∞
̅̅̅̅̅̅̅
𝑯𝟐∞).

Ans:-

𝐻 = 400𝑥1 + 600𝑥2 + 𝑥1 𝑥2 (40𝑥1 + 20𝑥2 )


Replacing x2 by 1-x1 in the above equation,we get

𝐻 = 600 − 180𝑥1 − 20𝑥13


𝑑𝐻
𝑑𝑥1
= −180 − 60𝑥12

We know,
𝑑𝐻
𝐻1 = 𝐻 + 𝑥2
𝑑𝑥1

𝑑𝐻
Substitution of H and in the above equation gives,
𝑑𝑥1

𝐻1 = 600 − 180𝑥1 − 20𝑥13 − 180𝑥2 − 60𝑥12 𝑥2


Replacing x2 by 1-x1 and simplifying, we get

𝐻1 = 420 − 60𝑥12 + 40𝑥13


Again we know,
𝑑𝐻
𝐻2 = 𝐻 − 𝑥1 𝑑𝑥1
𝑑𝐻
Substituting H and 𝑑𝑥1 in the above equation, we get

𝐻2 = 600 + 40𝑥13

Now, H1= lim 𝐻1 = 400 J/mol


𝑥1→1

H2= lim 𝐻2 = 600 J/mol


𝑥1→1

The infinite dilution property can be calculated as


̅̅̅̅̅̅̅= lim 𝐻1 = 420 J/mol
𝐻1∞
𝑥1→0

̅̅̅̅̅̅̅= lim 𝐻1
𝐻2∞ ̅̅̅̅ = 640 J/mol
𝑥2→0
2. In a binary solution if one component obeys Henry's law the other must obey L-R rule and vice
versa: justify…. (7)

> For a binary solution at constant temperature and pressure we may write

𝑥1 𝑑𝜇1 + 𝑥2 𝑑𝜇2 = 0 ….(1)

We know 𝑑𝜇𝑖 = 𝑅𝑇 𝑑𝑙𝑛𝑓̂̂̂𝑖 (at constant temperature) ……(2)

Combining equation (1) & (2) we obtain,

𝑥1 𝑑𝑙𝑛𝑓̂̂̂1 + 𝑥2 𝑑𝑙𝑛𝑓̂̂̂2 = 0 ….(3)

Upon dividing by 𝑑𝑥1 , equation (3) becomes


𝑑𝑙𝑛𝑓̂̂̂1 𝑑𝑙𝑛𝑓̂̂̂2
𝑥1 + 𝑥2 =0
𝑑𝑥1 𝑑𝑥1

𝑑𝑓̂̂̂1⁄𝑑𝑥1 𝑑𝑓̂̂̂2⁄𝑑𝑥2
𝑜𝑟, 𝑥1 = 𝑥2
𝑓̂̂̂1 𝑓̂̂̂2

𝑑𝑓̂̂̂1⁄𝑑𝑥1 𝑑𝑓̂̂̂2⁄𝑑𝑥2
𝑜𝑟, = … (4)
𝑓̂̂̂1⁄𝑥1 𝑓̂̂̂2⁄𝑥2
In the limit as 𝑥1 → 1 𝑎𝑛𝑑 𝑥2 → 0

𝑑𝑓̂̂̂1⁄𝑑𝑥1 𝑑𝑓̂̂̂2⁄𝑑𝑥2
lim = lim
̂1⁄𝑥1
𝑥1 →1 𝑓̂̂ ̂2⁄𝑥2
𝑥2 →0 𝑓̂̂

Since 𝑓̂̂̂1 = 𝑓̂̂1 when 𝑥1 = 1,this may be written as

1 𝑑𝑓̂̂̂1 (𝑑𝑓̂̂̂2 ⁄𝑑𝑥2 )⃒𝑎𝑡 𝑥2=0


(𝑓̂̂ ) ⃒𝑎𝑡 𝑥1 =1 = lim (𝑓̂̂̂2 ⁄𝑥2 )
1 𝑑𝑥1
𝑥2 →0

Let, LHS=RHS=1, which means component 1 satisfies L-R rule, as

𝑑𝑓̂̂̂1
( ) = 𝑓̂̂1 … . (5)
𝑑𝑥1 𝑎𝑡 𝑥1 =1

Now by RHS=1, we get, lim (𝑓̂̂̂2 ⁄𝑥2 ) = (𝑑𝑓̂̂̂2 ⁄𝑑𝑥2 )𝑎𝑡 𝑥2 =0 ….(6)
𝑥2 →0

Equation (6) represents nothing but Henry's law. From these derivations we conclude that when
Henry's law is valid for one species in a binary solution the Lewis Randall rule is valid for the other
species.
Assignment on Thermodynamics
By Rajdeep Mullick (Roll 28) & Sampan Sengupta (Roll 26)

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


activity coefficient.

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.

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 (𝒑𝑺𝒂𝒕
𝟏 )
-3 𝑺𝒂𝒕
& 249.5 x 10 bar (𝒑𝟐 ) 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 ---

𝑦𝑖 𝜋𝑎𝑖𝑉 = 𝑎𝑖𝑠𝑎𝑡 𝑥𝑖 𝛾𝑖 𝑃𝑖𝑠𝑎𝑡

where π = total pressure and 𝑎𝑖𝑉 and 𝑎𝑖𝑠𝑎𝑡 are fugacity coefficient of vapor and
saturated vapor respectively. [3+6+6=15]

Solutions:

1. At constant temperature and pressure, the Gibbs-Duhem relation is ---


∑𝑁 ̅
𝑖=1 𝑥𝑖 𝜕𝑀𝑖 = 0 ……………………………. (1a)
Where, 𝑥𝑖 = Mole fraction of ith component in the mixture
𝑀̅𝑖 = Partial molar property of the ith component
Now, the Activity Coefficient is related to excess Gibbs free energy by the following
relation,
𝑛 𝐺𝐸
𝜕( 𝑖 ⁄𝑅𝑇)
ln ∅𝑖 = [ 𝜕𝑛𝑖
] …………………… (1b)
𝑃,𝑇,𝑛𝑗
ln ∅𝑖 is a partial molar property, hence it will satisfy Gibbs-Duhem relation. So,
∑𝑁𝑖=1 𝑥𝑖 𝜕 ln ∅𝑖 = 0 ………… (1c)
Equation (1c) is the required relation.
2. We know from Raoult’s Law, 𝑦𝑖 𝑃 = 𝑥𝑖 𝑃𝑖𝑠
𝑦1 𝑃
Therefore, 𝑥1 = 𝑃1𝑠
……………………………………… (2a)

𝑦2 𝑃
𝑥2 = 𝑃2𝑠
.……………………………………... (2b)

& also at dew point pressure, ∑ 𝑥𝑖 = 1 …………. (2c)

Hence, from the above three equations we have,


𝑦1 𝑃 𝑦2 𝑃
𝑃1𝑠
+ 𝑃2𝑠
=1 …………………………. (2d)

1
Or, 𝑃= 𝑦1 𝑦2 …………………………………… (2e)
+
𝑃𝑠1 𝑃𝑠2

Given, 𝑦1 = 𝑦2 = 0.5 ; 𝑃1𝑆 = 1530 𝑚𝑚𝐻𝑔 ; 𝑃2𝑆 = 640 𝑚𝑚𝐻𝑔

Putting these values in equation (2e) we have,


1
𝑃= 0.5 0.5 𝑚𝑚𝐻𝑔 = 902.5 𝑚𝑚𝐻𝑔
+
1530 640

Therefore, the required dew point pressure is 902.5 mmHg.

3. Given,
𝑦𝑖 𝜋𝑎𝑖𝑉 = 𝑎𝑖𝑠𝑎𝑡 𝑥𝑖 𝛾𝑖 𝑃𝑖𝑠𝑎𝑡 ………….. (3a)

Considering ideal gas state,

𝑎𝑖𝑉 = 𝑎𝑖𝑠𝑎𝑡 = 1

Hence the equation (3a) becomes,

𝑦𝑖 𝜋 = 𝑥𝑖 𝛾𝑖 𝑃𝑖𝑠𝑎𝑡 ……………………… (3b)

Total pressure, 𝜋 = 𝑥1 𝛾1 𝑃1𝑠𝑎𝑡 + 𝑥2 𝛾2 𝑃2𝑠𝑎𝑡 …….... (3c)

Now, 𝑥1 = 0.2 ; 𝑥2 = (1 − 0.2) = 0.8

𝛾1 = 2.831 ; 𝛾2 = 1.1716

𝑃1𝑠 = 4.306 × 10−3 𝑏𝑎𝑟 ; 𝑃2𝑠 = 249.5 × 10−3 𝑏𝑎𝑟

Putting all these values in equation (3c) we have,

𝜋 = 0.2363 𝑏𝑎𝑟
Now, from equation (3b) we have,

𝑥 𝛾 𝑃 𝑠𝑎𝑡 −3
𝑦1 = ( 1 1 1 ⁄𝜋) = (0.2 × 2.831 × 4.306 × 10 ⁄0.2363)

𝒚𝟏 = 𝟎. 𝟎𝟏 , 𝒊. 𝒆; 𝟏 𝒎𝒐𝒍%
Thermodynamic Assignment
Submitted by:-Rima Parui (21) and Rahul Roy (18)
6th semester
Q. From a set of experimental VLE data of P-x1-y1 for methyl ethyl ketone(1)/toluene(2) system at 50 ℃.
Calculate the liquid phase properties:

a) 𝒇̂𝒍𝟏 , 𝒇𝒍𝟐 𝜸1 , 𝜸2
𝑮𝑬 𝑮𝑬
b)𝑹𝑻 , 𝑹𝑻𝒙𝟏 𝒙𝟐

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

P(kPa) 𝒙𝟏 𝒚𝟏
12.3(𝑃2𝑠𝑎𝑡 ) 0 0
15.51 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)

Solution: We know for non-ideal solution,

𝑓̂̂̂𝑖𝑣 =𝜑̂𝑖 𝑦𝑖 𝑃

𝑓̂̂̂𝑖𝑙 =𝛾𝑖 𝑥𝑖 𝑓̂̂𝑖

At low pressure, 𝜑̂𝑖 =1 and 𝑓̂̂𝑖 =𝑃𝑖𝑠

So, 𝑓̂̂̂𝑖𝑣 =𝑦𝑖 𝑃… …………………………………….(1)

Now at equilibrium, 𝑓̂̂̂𝑖𝑙 =𝑓̂̂̂𝑖𝑣

So, 𝑓̂̂̂𝑖𝑙 =𝑦𝑖 𝑃

And again 𝑦𝑖 𝑃=𝛾𝑖 𝑥𝑖 𝑃𝑖𝑠


𝑦𝑖 𝑃
Therefore, 𝛾𝑖 = ……………………………………….(2)
𝑥𝑖 𝑃𝑖𝑠

𝑓̂̂̂𝑖𝑣 =fugacity of component i in the vapor phase

𝑓̂̂̂𝑖𝑙 =fugacity of component i in liquid phase

𝑥𝑖 =mole fraction of i in the liquid phase


𝑦𝑖 =mole fraction of i in the vapor phase

𝛾𝑖 =activity coefficient of component i

𝜑̂𝑖 =fugacity coefficient of i in solution

𝑃𝑖𝑠 =saturated vapor pressure of component i in pure state at existing temperature.

Using equation (1) and (2) we can calculate 𝑓̂̂̂1𝑙 , 𝑓̂̂2𝑙 , 𝛾1 𝑎𝑛𝑑 𝛾2.

For binary mixture 𝑦1 + 𝑦2 = 1

Calculations are given below:

P(kPa) 𝒙𝟏 𝒚𝟏 𝒇̂𝒍𝟏 =𝒚𝟏 𝑷 𝒇𝒍𝟐 =𝒚𝟐 𝑷 𝜸𝟏 𝛄𝟐. 𝑮𝑬 𝑮𝑬


𝑹𝑻 𝑹𝑻𝒙𝟏 𝒙𝟐
12.3 0 0 0 12.300 - 1.0 0 -
15.51 0.0895 0.2716 4.212 11.298 1.304 1.009 0.032 0.389
18.61 0.1981 0.4565 8.496 10.114 1.188 1.026 0.054 0.342
21.63 0.3195 0.5934 12.835 8.795 1.114 1.050 0.068 0.312
24.01 0.4232 0.6815 16.363 7.697 1.071 1.078 0.072 0.297
25.92 0.5119 0.7440 19.284 6.636 1.044 1.105 0.071 0.283
27.96 0.6096 0.8050 22.508 5.542 1.023 1.135 0.063 0.267
30.12 0.7135 0.8639 26.021 4.099 1.010 1.163 0.051 0.248
31.75 0.7934 0.9048 28.727 3.023 1.003 1.189 0.038 0.234
34.14 0.9102 0.9590 32.750 1.400 0.997 1.268 0.019 0.227
36.09 1 1 36.090 0.000 1.000 - 0 -
Assignment on thermodynamics.
Submitted by,
Arnab Bandyopadhyay (37)
Dolan Bijali (32)
Q.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 25°c must be mixed to form the 2000cm3
of anti-freeze also at 25°c.
Partial molar volumes for methanol, water in 30mole% methanol solution and their pure species
molar volumes both at 25°c ---
Methanol(1) ̅𝑣1
̅̅̅ = 38.632 cm3mol-1 V1 = 40.727 cm3mol-1
Water(2) ̅̅̅̅ = 17.175 cm3mol-1
𝑣2 V2= 18.068 cm3mol-1

Ans.
The molar volume of binary antifreeze solution and known values of partial volumes and mole
fractions are related as,
̅̅̅̅ + x2𝑣2
V = x1𝑣1 ̅̅̅̅ = (0.3*38.632)+ (0.7*17.765) = 24.025 cm3mol-1

The required total volume of solution is Vt = 2000 cm3 , so the number of mole of solution required is
n =( Vt/V) =( 2000/24.025) = 83.246 mol
of this, 30% is methanol and 70% is water :
n1 = (0.3*83.246) = 24.974 mol and n2 = (0.7*83.246) = 58.272 mol
The volume of each pure species is Vti = niVi, Thus,
Vt1 = (24.974*40.727) = 1017 cm3 Vt2 = (58.272*18.068) = 1053 cm3 .

Q.2
What is Poynting factor ? Derive the equation-
𝑣𝑙𝑖 (𝑃−𝑃𝑠𝑎𝑡
𝑖 )
𝑓̂̂𝑖 = 𝜑𝑖𝑠𝑎𝑡 𝑃𝑖𝑠𝑎𝑡 exp{ 𝑅𝑇
}

Ans.
The fugacity of pure species I as a compressed liquid may be calculated from the product of easily
evaluated ratio:
𝑓̂̂𝑖𝑣 (𝑃𝑖𝑠𝑎𝑡 ) 𝑓̂̂𝑖𝑙 (𝑃𝑖𝑠𝑎𝑡 ) 𝑓̂̂𝑖𝑙 (𝑃)
𝑓̂̂𝑖𝑙 (𝑃) = 𝑃𝑖𝑠𝑎𝑡 𝑓̂̂𝑖𝑣 (𝑃𝑖𝑠𝑎𝑡 ) 𝑙 𝑠𝑎𝑡 𝑃𝑖𝑠𝑎𝑡
𝑓̂̂𝑖 (𝑃𝑖 )

Let assume the ratios are A,B,C respectively. Ratio A is the vapor phase fugacity coefficient of pure
vapor I at its vapor/liquid saturation pressure, designated ∅𝑖𝑠𝑎𝑡 . It is given by
𝑃𝑠𝑎𝑡 𝑑𝑃
𝑙𝑛∅𝑖𝑠𝑎𝑡 = ∫0 𝑖 (𝑍𝑣𝑖 − 1) (const T)
𝑃
The ratio (B) is unity. Ratio (C) reflects the effect of pressure on the fugacity of pure liquid i.
We can derive it from the relation 𝑑𝐺 = 𝑉𝑑𝑃 − 𝑆𝑑𝑇 (𝑐𝑜𝑛𝑠𝑡 𝑇), which gives
𝑃
𝐺𝑖 − 𝐺𝑖𝑠𝑎𝑡 = ∫ 𝑉𝑖𝑙 𝑑𝑃
𝑃𝑖𝑠𝑎𝑡

Another expression for this difference results as


𝑓̂̂𝑖
𝐺𝑖 − 𝐺𝑖𝑠𝑎𝑡 = 𝑅𝑇𝑙𝑛
𝑓̂̂𝑖𝑠𝑎𝑡
From those two equations we get,
𝑓̂̂𝑖 1 𝑃 𝑙
𝑙𝑛 = ∫ 𝑉 𝑑𝑃
𝑓̂̂𝑖𝑠𝑎𝑡 𝑅𝑇 𝑃𝑠𝑎𝑡 𝑖
𝑖

𝑓̂̂𝑖𝑙 (𝑃) 1 𝑃
Ratio (C) is then 𝑙 𝑠𝑎𝑡 = 𝑒𝑥𝑝 𝑅𝑇 ∫𝑃𝑠𝑎𝑡 𝑉𝑖𝑙 𝑑𝑃
𝑓̂̂𝑖 (𝑃𝑖 ) 𝑖

Substituting for three ratios in the initial equation yields


1 𝑃 𝑙
𝑓̂̂𝑖 = ∅𝑖𝑠𝑎𝑡 𝑃𝑖𝑠𝑎𝑡 𝑒𝑥𝑝 ∫ 𝑉 𝑑𝑃
𝑅𝑇 𝑃𝑠𝑎𝑡 𝑖
𝑖

Because an excellent approximation is often obtained when 𝑉𝑖𝑙 is assumed constant at the value for
saturated liquid. In this case,

𝑠𝑎𝑡 𝑠𝑎𝑡 𝑉𝑖𝑙 (𝑃 − 𝑃𝑖𝑠𝑎𝑡 )


𝑓̂̂𝑖 = ∅𝑖 𝑃𝑖 𝑒𝑥𝑝
𝑅𝑇
The exponential function is called Poynting factor.
Q.3
𝑛𝐺𝑅
𝜕( )
𝑅𝑇
Prove that 𝑙𝑛∅ = [ 𝜕𝑛𝑖
]𝑃,𝑇,𝑛𝑗

Ans.
From fundamental property relation we know that,
𝑛𝐺 1 𝑛𝐺
𝑑( )= 𝑑(𝑛𝐺) − 𝑑𝑇
𝑅𝑇 𝑅𝑇 𝑅𝑇 2
Again we know that, 𝑑(𝑛𝐺) = 𝑉𝑑𝑃 − 𝑆𝑑𝑇 + ∑𝑖 µ𝑖 𝑑𝑛𝑖
And G=H-TS
𝑛𝐺 𝑛𝑉 𝑛𝐻 𝐺̅
Now from this relation we can achieve that 𝑑 (𝑅𝑇 ) = 𝑅𝑇
𝑑𝑃 − 𝑅𝑇 2
𝑑𝑇 + ∑𝑖 𝑅𝑇𝑖 𝑑𝑛𝑖

This relation is for general case. For ideal case we can write that,
𝑖𝑔
𝑛𝐺 𝑖𝑔 𝑛𝑉 𝑖𝑔 𝑛𝐻 𝑖𝑔 𝐺̅𝑖
𝑑( )= 𝑑𝑃 − 𝑑𝑇 + ∑ 𝑑𝑛𝑖
𝑅𝑇 𝑅𝑇 𝑅𝑇 2 𝑅𝑇
𝑖

Subtracting those two relation we get,


𝑅
𝑛𝐺 𝑅 𝑛𝑉 𝑅 𝑛𝐻 𝑅 𝐺̅𝑖
𝑑( )= 𝑑𝑃 − 𝑑𝑇 + ∑ 𝑑𝑛
𝑅𝑇 𝑅𝑇 𝑅𝑇 2 𝑅𝑇 𝑖
𝑖

This is the fundamental residual property.


𝐺𝑖̅ 𝑅
Again we know that fugacity coefficient 𝑙𝑛∅ =
𝑅𝑇

So we get,
𝑛𝐺 𝑅 𝑛𝑉 𝑅 𝑛𝐻 𝑅
𝑑( )= 𝑑𝑃 − 𝑑𝑇 + ∑ 𝑙𝑛∅ 𝑑𝑛𝑖
𝑅𝑇 𝑅𝑇 𝑅𝑇 2
𝑖

Keeping constant P,T,nj and differentiating with respect to dni we get our required relation
𝑛𝐺 𝑅
𝜕( )
𝑅𝑇
𝑙𝑛∅ = [ ]
𝜕𝑛𝑖 𝑃,𝑇,𝑛𝑗
Thermodynamics Assignment

Submitted by: - Rajath Goswami-45, Bapan Halder-43.

Q1.) Show that in a binary mixture, if one component obeys Henry’s law then the other component
must follow the L-R rule.

Soln:-

In a binary solution, at constant temperature and pressure, we may write

x1d𝜇1 +x2d𝜇2 =0

We know, d𝜇𝑖 =RTln 𝑓̂̂̂𝑖 (at constant temperature)

𝑑 ln 𝑓̂̂̂1 𝑑 ln 𝑓̂̂̂
Thus, x1 𝑑𝑥1
+x2 𝑑𝑥 2 =0
2

𝑑𝑓̂1 𝑑𝑓̂2
𝑑𝑥1 𝑑𝑥2
=> x1 𝑓̂̂̂1
=x2 𝑓̂̂̂2

𝑑𝑓̂1 𝑑𝑓̂2
𝑑𝑥1 𝑑𝑥2
=> 𝑓̂1
= 𝑓̂2
𝑥1 𝑥2

In the limit as x1→ 1 and x2→0, we have

𝑑𝑓̂1 𝑑𝑓̂2
𝑑𝑥1 𝑑𝑥2
lim 𝑓̂1
= lim 𝑓̂2
𝑥1→1 𝑥2→0
𝑥1 𝑥2

Since 𝑓̂̂̂1=𝑓̂̂1 when 𝑥1 →1 this may be written as

2⌋ 𝑑𝑓̂
1 𝑑𝑓̂̂̂1 𝑑𝑥2 𝑥2=0

𝑓̂̂1 𝑑𝑥1 𝑥1=1
= 𝑓̂
lim 2
𝑥 →0 𝑥2
2

Let LHS=RHS, which means component satisfies L-R rule, as

𝑑𝑓̂̂̂1
⌋ =𝑓̂̂
𝑑𝑥1 𝑥1=1 1

Now by RHS=1, we get

𝑓̂̂̂2 𝑑𝑓̂̂̂2
lim = ⌋𝑥
𝑥2→0 2 𝑑𝑥2 2=0
𝑥

The above equation is nothing but Henry’s law.

Thus the derivation concludes that when one component follows Lewis Randall rule, the other must
follow Henry’s law.
Q2.) Prove a relation with 𝛾𝑖 and 𝑥𝑖 in a methyl ethyl ketone (1)/ toluene (2) solution at 50° c binary
solution.

Soln:-

𝑓̂̂̂ 𝑓̂̂̂
We know that, 𝛾𝑖 ≡ 𝑓̂̂ 0𝑖𝑥 , and by LR rule we have 𝛾𝑖 ≡ 𝑓̂̂ 𝑥𝑖 . When 𝛾𝑖 =1, we may confirm that L-R rule is
𝑖 𝑖 𝑖 𝑖
valid. This result is obtained at 𝑥𝑖 =1. More over differentiating at constant temperature and pressure
we have,

𝑑𝛾𝑖 1 1 𝑑𝑓̂̂̂𝑖 𝑓̂̂̂


= (
𝑑𝑥𝑖 𝑓̂̂𝑖 𝑥𝑖 𝑑𝑥𝑖
− 𝑥𝑖2 )
𝑖

In the limit as 𝑥𝑖 →1, 𝑓̂̂̂𝑖 →𝑓̂̂𝑖 and thus the above equation becomes

𝑑𝛾𝑖 1 𝑑𝑓̂̂̂

𝑑𝑥𝑖 𝑥𝑖 =0
=𝑓̂̂ (𝑑𝑥𝑖 ⌋𝑥𝑖=1 − 𝑓̂̂𝑖 )
𝑖 𝑖

𝑑𝑓̂̂̂ 𝑑𝛾𝑖
Now we know that 𝑑𝑥𝑖 ⌋𝑥𝑖=1 = 𝑓̂̂𝑖 , hence ⌋
𝑑𝑥𝑖 𝑥𝑖 =0
=0
𝑖

So we can conclude that the graph of 𝛾𝑖 vs 𝑥𝑖 curve approaches unity with zero slope at 𝑥𝑖 =1. This is
seen in figure below, where 𝛾1 and 𝛾2 values for methyl ethyl ketone (1)/toluene (2) solution at 50° c are
plotted as function of 𝑥1 .

Figure

The above figure shows that the slope of the curve becomes zero at the two extreme conditions i.e. at
𝑥𝑖 at zero and at one.
Assignment: Thermodynamics
Dipanjan Sarkar (Roll - 07) Biswadeep Mondal (Roll – 08)

1.1) Calculate the bubble point of a n-pentane / n-heptane solution at P=600 Torr and x1= 0.6
Given, Antoine equation constants:
Components A B C
n-pentane 6.87632 1075.78 233.205
n-heptane 6.9386 1264.37 216.640

Assume ideal solution mixture.

1.2) Draw T-x-y & P-x-y diagram of a Vapour-Liquid mixture. [10+5=15]

Solution:
1.1 P=600 Torr, x1= 0.6 (Given)
To calculate: T  Bubble Point Temperature
y1, y2  Mole fractions of components 1 & 2 in vapour phase

We know,
𝐵𝑖
ln 𝑃𝑖𝑠𝑎𝑡 = 𝐴𝑖 −
(𝐶𝑖 + 𝑇)
(equation 1)
𝐵𝑖
or, 𝑇= 𝐴𝑖 − ln 𝑃𝑖𝑠𝑎𝑡
− 𝐶𝑖

We calculate the individual saturation temperature of each component at the given system
pressure P=600 Torr , i.e.,
𝐵𝑖
𝑇𝑖𝑠𝑎𝑡 = − 𝐶𝑖
𝐴𝑖 − ln 𝑃

For n- pentane;

A1= 6.87632, Bi= 1075.78, Ci= 233.205

Therefore, T1Sat= 2010.85

For n-heptane;

A2=6.89386, B2=1264.37, C2=216.640

Therefore, T2Sat= 2327.721

Therefore, Told = x1 . T1Sat + x2 . T2Sat = 2137.6

This Told value is used as our initial guess value for the iterative process in calculation of
Bubble point T.

PSat1, old = exp( 6.87632 – 1075.78(2137.6 + 233.205)) = 615.576


PSat2, old = exp(6.89386 – 1264.37 (2137.6 + 216.640)) = 576.398

now,

Psat1, new = P/ ( x1 + x2 ( PSat2, old / PSat1, old)) [here, we have assumed ideal mixture, which
implies ℽi=1]

Therefore,

Psat1, new = 600/ (0 .6 + 0.4 ( 576.398 / 615.576))

= 615.673
Putting this vale of Psat1, new in eq-1, we get :
T1, new= 2138.427
For the next iteration, we set Told= T1, new and get the new T2, new = 2138.158
Similarly, T3, new = 2138.384 & T4, new = 2138.383
Thus, we can see that the temperature converges to a value of 2138.384, and the
corresponding saturation pressure Psat1 is 615.66

Therefore,

y1 = (x1 * Psat1 ) / P = 0.616

The net result is: Tbubble= 2138.38 ℃, y1= 0.616, y2= 0.384 (Answer)

1.2)

The above figures represent the P-X-Y diagram for three temperatures (Ta, Tb, Tc) while the
T-X-Y diagram represents for three different pressures (Pa, Pb, Pc).
Dotted lines represent saturated vapour line (dew lines) while the solid lines represent
saturated liquid (vapour line).
Assignment: Thermodynamics
Dipanjan Ghosh (Roll - 16) Rajeev Ranjan (Roll – 17)

1.1) Calculate the bubble point of a n-pentane (1) / n-heptane solution at P=600 Torr and x1= 0.6
Given, Antoine equation constants:
Components A B C
n-pentane 6.87632 1075.78 233.205
n-heptane 6.9386 1264.37 216.640
Assume ideal solution mixture.

1.2) Derive modified Raoult’s law from VLE. [10+5=15]

Solution:
1.2 P=600 Torr, x1= 0.6 (Given)
To calculate: T  Bubble Point Temperature
y1, y2  Mole fractions of components 1 & 2 in vapour phase

We know,
𝐵𝑖
ln 𝑃𝑖𝑠𝑎𝑡 = 𝐴𝑖 −
(𝐶𝑖 + 𝑇)
(equation 1)
𝐵𝑖
or, 𝑇= − 𝐶𝑖
𝐴𝑖 − ln 𝑃𝑖𝑠𝑎𝑡

We calculate the individual saturation temperature of each component at the given


system pressure P=600 Torr , i.e.,
𝐵𝑖
𝑇𝑖𝑠𝑎𝑡 = − 𝐶𝑖
𝐴𝑖 − ln 𝑃

For n- pentane;
A1= 6.87632, Bi= 1075.78, Ci= 233.205
Therefore, T1Sat= 2010.85
For n-heptane;
A2=6.89386, B2=1264.37, C2=216.640
Therefore, T2Sat= 2327.721
Therefore, Told = x1 . T1Sat + x2 . T2Sat = 2137.6
This Told value is used as our initial guess value for the iterative process in calculation
of Bubble point T.
PSat1, old = exp( 6.87632 – 1075.78(2137.6 + 233.205)) = 615.576
PSat2, old = exp(6.89386 – 1264.37 (2137.6 + 216.640)) = 576.398
now,
Psat1, new = P/ ( x1 + x2 ( PSat2, old / PSat1, old)) [here, we have assumed ideal mixture,
which implies ℽi=1]
Therefore,
Psat1, new = 600/ (0 .6 + 0.4 ( 576.398 / 615.576))
= 615.673
Putting this vale of Psat1, new in eq-1, we get :
T1, new= 2138.427
For the next iteration, we set Told= T1, new and get the new T2, new = 2138.158
Similarly, T3, new = 2138.384 & T4, new = 2138.383
Thus, we can see that the temperature converges to a value of 2138.384, and the
corresponding saturation pressure Psat1 is 615.66
Therefore,
y1 = (x1 * Psat1 ) / P = 0.616
The net result is: Tbubble= 2138.38 ℃, y1= 0.616, y2= 0.384 (Answer)

1.2)
The original Raoult’s law can be written as: 𝑦𝑖 𝑃 = 𝑥𝑖 𝑃𝑖 𝑠𝑎𝑡
Where i= 1, 2, 3…..
Now we take into account the deviation of solution ideal behaviour
𝑦𝑖 𝑃 = 𝛾𝑖 𝑥𝑖 𝑃𝑖 𝑠𝑎𝑡 (1)
Where 𝛾𝑖 = activity coefficient.
Activity coefficients are functions of temperature, pressure, liquid phase compositions and
experiments.

Using summation on both sides,


∑ 𝑦𝑖 𝑃 = ∑ 𝛾𝑖 𝑥𝑖 𝑃𝑖 𝑠𝑎𝑡 (2)
Or, 𝑃 ∑ 𝑦𝑖 = ∑ 𝛾𝑖 𝑥𝑖 𝑃𝑖 𝑠𝑎𝑡
Now, ∑ 𝑦𝑖 = 1

𝑃 = ∑ 𝛾𝑖 𝑥𝑖 𝑃𝑖 𝑠𝑎𝑡
Thermodynamics Assignment
Submitted by- Abesh Chatterjee (47) & Debrup Chakraborty (46)
Question
1. What is Retrograde Condensation? What are Maxcondenbar and Maxcondentherm? When
Retrograde condensation of 1st Kind and 2nd kind Occur?
[2+3+1]

2. A binary system consists of n- pentane (1) and n- hexane (2) at 30 ̊ C. Determine the
composition of vapour of the component (1) which is in equilibrium with a liquid containing 20-
mole % n-pentane (1) at 30 ̊ C.

GIVEN:
Saturated vapour pressure of n-pentane (1) at 30̊c P1v = 4.306 x 10-3 bar
Saturated vapour pressure of n-hexane (2) at 300c P2v = 249.5 x 10-3 bar
The activity coefficient of (1) & (2) at X1 = 0.2 at 30 C
̊ ,
ᵞ1= 2.831, ᵞ2= 1.1716
Assume that at low pressure, gases are in ideal state but the liquid phase is not use the
following equation:
yi π αiV = αisat xi. ᵞi.Pis
Where π = total pressure & αiV and αisat are the fugacity coefficient of vapour and saturated vapour
respectively. [9]

Solution

1.

 Retrograde Condensation: In binary/multi component system, the Critical Point does not
correspond highest temperature or pressure, as it is observed for single component system.
For binary/ multi component system, it can be observed, on condensing vapour phase,
formation of liquid begins from dew point; the amount increases upto a certain point, then
decreases continuously and at other end , the last drop of liquid is disappear, forming pure
vapour phase. This phenomenon in binary/ multi component system is known as Retrograde
Condensation.

 Maxcondenbar: Maximum pressure on P-T envelop from which point condensations


decreases continuously, is called Maxcondenbar (Mp). Maxcondentherm: Maximum
temperature on P-T envelop from which point condensations decreases
continuously, is called Maxcondentherm (Mt).
For a pure/ single component system, critical point, maxcondentherm, maxcondenbar
coincide and the unique point is referred as critical point. However, for binary/ multi
component system there are different possibilities of critical point with respect to
maxcondentherm or maxcondenbar.
 Retrograde condensation of 1st kind occurs when a constant temperature line twice crosses
the dew point curve.
Retrograde condensation of 2nd kind occurs when a constant pressure line twice crosses the
bubble point curve.

2.
Given, y1 π αiV = αisat xi ᵞi Pis … (1)
We know that the condition of ideal gas state
αiV = αisat = 1
Hence from equation (1)
y1 π = xi ᵞi Pis …..(2)
Total pressure π = Y1 +Y2
π = x1 ᵞ1 P1s + x2 ᵞ2 P2s …..(3)
x1= 0.2
x2 = 1- 0.2 = 0.8
ᵞ1 = 2.831
ᵞ2 = 1.1716
P2s = 4.306 x 10-3
P2s = 249.5 x 10-3
Put all these value in equation (3) we get
Π = 0.2363 bar
Now, from equation (2),
y1 = x1 ᵞ1 P1s / π
= 0.2 x 20831 x 4.306 x 10-3 /0.2363
= 0.01
i.e. 1 mol% (ans)
Name: Sumanta Goswami (39), Sourav Mondal (30)

1. Modified Roult’s law:


For low to moderate pressures a much more realistic equation for vapor liquid equillibrium
when the Roult’s law assumption is abandoned and account is taken of deviations from
ideality in the liquid phase. Modified Roult’s law results when γi, an activity coefficient is
inserted into Roult’s law:
Pγi = xiγi P where I = 1,2,3,…..N

2. P(bubl)= x1P1sat+ x2P2sat +x3P3sat


= 0.45*195.75+0.35*97.84+0.20*50.32
= 132.40 kPa
P(dew)= 1/(y1/P1sat +y2/P2sat+ y3/P3sat)
= 101.52 kPa
Because the given pressure lies between p(bubl) and P(dew) the system is in a two phase
region.and a flash calculation can be made.
Ki=Pisat/P
K1= 1.7795, k2= 0.8895, k3= 0.4575
Now we know,

∑Ziki /(1+ν(ki-1)) =1

[0.45*1.7795/(1+0.7795ν)]+ [0.35*0.8895/(1-0.1105ν)] +[0.2*0.4575/(1-0.5425ν)] =1


………(eq.1)
ν=0.7364
hence, L, the moles of the liquid= 1-ν =0.2636 moles

now yi =Ziki/ (1+ν(ki-1))

thus each term of left side of the eq.1 become


y1=0.5087, y2= 0.3389, y3=0.1524

now xi=yi/ki
x1= 0.2859, x2 =0.3810, x3= 0.3331

∑xi=1 and ∑ yi=1


3.
Arghyadeep Paul(Roll-9), Amartya Ghosh (Roll-10)-Thermodyanamics Assignment
Q1.) Show that in a binary mixture, if one component obeys Henry’s law then the other component
must follow the L-R rule.
Soln:-
In a binary solution, at constant temperature and pressure, we may write
x1d𝜇1 +x2d𝜇2 =0

We know, d𝜇𝑖 =RTln 𝑓̂̂̂𝑖 (at constant temperature)

𝑑 ln 𝑓̂̂̂1 𝑑 ln 𝑓̂̂̂2
Thus, x1 +x2 =0
𝑑𝑥1 𝑑𝑥2
̂1
𝑑𝑓 ̂2
𝑑𝑓
𝑑𝑥1 𝑑𝑥2
=> x1 =x2
𝑓̂̂̂1 𝑓̂̂̂2
𝑑𝑓̂1 𝑑𝑓̂2
𝑑𝑥1 𝑑𝑥2
=> 𝑓̂1 = ̂2
𝑓
𝑥1 𝑥2

In the limit as x1→ 1 and x2→0, we have

𝑑𝑓̂1 𝑑𝑓̂2
𝑑𝑥1 𝑑𝑥2
lim 𝑓̂1 = lim 𝑓̂2
𝑥1→1 𝑥2→0
𝑥1 𝑥2

Since 𝑓̂̂̂1 =𝑓̂̂1 when 𝑥1 →1 this may be written as


̂2
𝑑𝑓
1 𝑑𝑓̂̂̂1 ⌋
𝑑𝑥2 𝑥2=0
⌋ =
𝑓̂̂1 𝑑𝑥1 𝑥1=1 lim
̂2
𝑓
𝑥 →0 𝑥2
2
Let LHS=RHS, which means component satisfies L-R rule, as

𝑑𝑓̂̂̂1
⌋ =𝑓̂̂
𝑑𝑥1 𝑥1=1 1
Now by RHS=1, we get

𝑓̂̂̂2 𝑑𝑓̂̂̂2
lim = ⌋𝑥
𝑥2→0 𝑥2 𝑑𝑥2 2=0

The above equation is nothing but Henry’s law.


Thus the derivation concludes that when one component follows Lewis Randall rule, the other must
follow Henry’s law.
2. (1) (2)

MeOH-H2O system

𝑥1 = 0.5 mole fraction of CH3OH in liquid Phase


𝑦1 = 0.8 mole fraction of CH3OH in vapor phase.
𝑥2 = 0.5 mole fraction of H2O in liquid phase
𝑦2 = 0.2 mole fraction of H2O in vapor phase. T = 60◦ C
𝑣𝑎𝑝
𝑝𝐴 = 85 kPa, vapor pressure of CH3OH P = 60 kPa
𝑣𝑎𝑝
𝑝𝐵 = 20 kPa, vapor pressure of H2O

Now,
𝑣𝑎𝑝 Where 𝛾2 = activity co-efficient of water in liquid phase
𝑦2 𝑝 = 𝑥2 𝛾2 𝑝𝐵

0.2 × 60 = 0.5 × 𝛾2 × 20
∴ 𝛾2 = 1.2
The activity co-efficient of water in liquid phase is 1.2.

We know,
𝑔𝐸 = 𝑅𝑇[𝑥1 ln 𝛾1 + 𝑥2 ln 𝛾2 ] (𝑔𝐸 = 𝐸𝑥𝑐𝑒𝑠𝑠 𝐺𝑖𝑏𝑏𝑠 𝑓̂̂𝑟𝑒𝑒 𝑒𝑛𝑒𝑟𝑔𝑦)
Again,
𝑣𝑎𝑝
𝑦1 𝑝 = 𝑥1 𝛾1 𝑝𝐴

60 × 0.5 = 0.5 × 𝛾1 × 8.5


60 × 0.8
∴ 𝛾1 =
0.5 × 8.5
=1.129
∴ 𝑔𝐸 = 8.314 𝐽 𝑚𝑜𝑙 −1 𝑘 −1 × (273 + 60)𝐾 × [0.5 ln 1.129 + 0.5 ln 1.2 ]
(2.768.56 × 0.1518) 𝐽𝑚𝑜𝑙 −1

= 420.34 𝐽𝑚𝑜𝑙 −1

Therefore, the excess Gibbs free energy in liquid mixture is 420.34 𝐽𝑚𝑜𝑙 −1.
SOUMEN DAS AND AKHIL KR GOLU(ROLL-12 AND 13)
Q1)The fugacity of component 1 in binary liquid mixture of component 1and 2 at 298 k and 20 bar

is given by : ƒ1/=50x1 – 80x12 + 40x13


Where ƒ1 is in bar and x1is the mole fraction of component 1 determine :

a) The fugacity ƒ1 of pure component 1.


b) The fugacity coefficient Ø1
c) The Henry’s law constant K1
d) The activity coefficient µ1

Solution:

a) When the mole fraction approaches unity. The fugacity of a component in the solution
becomes equal to the fugacity of pure component .that is , ƒ1=ƒ/1 when x1.
Therefore ,ƒ1=50(1) – 80(1)2 + 40(1)3
= 50 – 80 + 40
= 10 bar
b) Ø1 =ƒ1 /P = 10/20 =0.5
c) We know that ,Henry’s law constant is-
K1 = lim ( ƒ//x1) = lim ( ƒ//x1) =(50 – 80x1 +40 x12)
X1→0 x1→0
= 50
So henry’s law constant is 50 bar

d) µ1 = ƒ1// (x1 ƒ) = (50x1 – 80 x12 + 40x13)/10x1

= 5 – 8x1 + 4x12

Q2) Define Activity coefficient . How do you distinguish between the activity coefficient based on
the Lewis Randall rule and that based on the dilute solution .

Activity coefficient : Activity coefficient is a factor which is measure the extent to which the real
solution departs from ideality.

The first conforms to Lewis –Randall rule in which case ƒ10 =ƒ1 ,the fugacity of the pure species at the
system pressure and second type conforms to an ideal dilute solution behaviour (the henry’s law),in
which case ƒi0=Ki , the henry’s law constant . depending upon the standard states on which they are
based the activity coefficients can take different numerical values.

Q3) derive effect of pressure on activity coefficients.


𝝏𝒍𝒏ƒ𝒊 𝑽𝒊
The effect of pressure on fugacity is ( )T = -----------------------------------(eqn 1)
𝝏𝑷 𝑹𝑻

Here ƒi is the fugacity of pure i and Vi is its molar volume .in a similar way it can be shown that
ƒi/ , the fugacity of i in solution varies with pressure according to
/ /
𝝏ƒ𝒊 𝑽𝒊
(
𝝏𝑷
)T =
𝑹𝑻
---------------------------------------(eqn 2)
To combining equation 1 and equation 2 ,we get
/
ƒ
𝝏𝒍𝒏 𝒊⁄ƒ /
𝑽𝒊 −𝑽𝒊
𝒊
( )T = ---------------------------------- (EQn 3)
𝝏𝑷 𝑹𝑻

From the state of Lewis Randall rule , we get


/
ƒ𝒊⁄
ƒ𝒊 = 𝜸𝒊 𝒙𝒊 so that( eqn 3) can be written as
/
𝝏𝒍𝒏𝜸𝒊 𝒙𝒊 𝑽𝒊 −𝑽𝒊
( )T =
𝝏𝑷 𝑹𝑻
𝝏𝒍𝒏𝒙𝒊
As mole fraction 𝒙𝒊 is independent of pressure ( )T =0 and hance
𝝏𝒑

/
𝝏𝒍𝒏𝜸𝒊 𝑽𝒊 −𝑽𝒊
( )T =
𝝏𝑷 𝑹𝑻
/
The molar volumes 𝑽𝒊 and 𝑽𝒊 correspond to the particular phase under consideration .for
liquid solutions , the effect of pressure on activity coefficient is negligible at pressures below
atmospheric .