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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).
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)
𝑃 = ∑ 𝛾𝑖 𝑥𝑖 𝑃𝑖 𝑠𝑎𝑡
Thermodynamics Assignment
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
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.
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.
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 ---
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 ,
Vig = RT/P ,
Hence dGi-dGiig=(Vi-Viig)dP
Or, dGiR=ViRdP
ViR=(ZiRT/P)-(RT/P)
= RT(Zi-1) /P
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 ?
= 1.00735
⌠1 = 2.7385
Or, ⌠2=1.2344
Here A and B are the Van Leer constants for species 1 and 2
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 .
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
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
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
Now 𝑃1𝑠𝑎𝑡
𝑛𝑒𝑤 = 79.42581419
T1new = 3643.31/(16.59158-ln𝑃1𝑠𝑎𝑡
𝑛𝑒𝑤 ) + 33.424 = 331.6464
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
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:-
ΔSmixing= -RΣyilnyi
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
components Ai Bi Ci
n-pentane(1) 6.87632 1075.78 233.205
n-heptane(2) 6.89386 1264.37 216.640
Solution:
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
𝑇1𝑠𝑎𝑡 = 2010.854
1264.37
𝑇2𝑠𝑎𝑡 = 6.89386−𝑙𝑛(600) − 216.640
𝑇2𝑠𝑎𝑡 = 2327.721
𝑇 = ∑ 𝑥𝑖 𝑇𝑖𝑠𝑎𝑡
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
𝑃 = 𝑥1 𝛾1 𝑝1𝑠𝑎𝑡 + 𝑥2 𝛾2 𝑝2𝑠𝑎𝑡
𝑃
𝑝1𝑠𝑎𝑡 = 𝑝𝑠𝑎𝑡 --------------------(3)
𝑥1 𝛾1 +𝑥2 𝛾2 ( 2𝑠𝑎𝑡 )
𝑝1
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 ℃
𝑠𝑎𝑡
𝑝1(𝑜𝑙𝑑) = 622.985
𝑠𝑎𝑡
𝑝2(𝑜𝑙𝑑) =584.675
𝑠𝑎𝑡
𝑝1(𝑛𝑒𝑤) =622.986
(3)
And hence, 𝑇𝑛𝑒𝑤 =2201.810 ℃
𝑠𝑎𝑡
𝑝1(𝑜𝑙𝑑) = 622.986
𝑠𝑎𝑡
𝑝2(𝑜𝑙𝑑) =584.676
𝑠𝑎𝑡
𝑝1(𝑛𝑒𝑤) =622.986
(4)
And hence, 𝑇𝑛𝑒𝑤 =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
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:
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 .
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
Given, ɣ1 = 1.40; ɣ2 =1.25; x1 =0.25; x2 =0.75, determine the constants B* & A*.
Let (A*/B*) = β
So,2.007 β2+1.338β(0.223-B*)=0………………………………………….eq(4)
[(-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)
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
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.
ii. What is the excess Gibb’s free energy (𝒈𝑬 𝒊𝒏 𝑱/𝒎𝒐𝒍) of liquid mixture?
SOLUTION:
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
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>
MeOH-H2O system
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,
= 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)
Ans:-
We know,
𝑑𝐻
𝐻1 = 𝐻 + 𝑥2
𝑑𝑥1
𝑑𝐻
Substitution of H and in the above equation gives,
𝑑𝑥1
𝐻2 = 600 + 40𝑥13
̅̅̅̅̅̅̅= 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
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
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)
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 ---
where π = total pressure and 𝑎𝑖𝑉 and 𝑎𝑖𝑠𝑎𝑡 are fugacity coefficient of vapor and
saturated vapor respectively. [3+6+6=15]
Solutions:
𝑦2 𝑃
𝑥2 = 𝑃2𝑠
.……………………………………... (2b)
1
Or, 𝑃= 𝑦1 𝑦2 …………………………………… (2e)
+
𝑃𝑠1 𝑃𝑠2
3. Given,
𝑦𝑖 𝜋𝑎𝑖𝑉 = 𝑎𝑖𝑠𝑎𝑡 𝑥𝑖 𝛾𝑖 𝑃𝑖𝑠𝑎𝑡 ………….. (3a)
𝑎𝑖𝑉 = 𝑎𝑖𝑠𝑎𝑡 = 1
𝛾1 = 2.831 ; 𝛾2 = 1.1716
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)
𝑓̂̂̂𝑖𝑣 =𝜑̂𝑖 𝑦𝑖 𝑃
Using equation (1) and (2) we can calculate 𝑓̂̂̂1𝑙 , 𝑓̂̂2𝑙 , 𝛾1 𝑎𝑛𝑑 𝛾2.
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
𝑓̂̂𝑖𝑙 (𝑃) 1 𝑃
Ratio (C) is then 𝑙 𝑠𝑎𝑡 = 𝑒𝑥𝑝 𝑅𝑇 ∫𝑃𝑠𝑎𝑡 𝑉𝑖𝑙 𝑑𝑃
𝑓̂̂𝑖 (𝑃𝑖 ) 𝑖
Because an excellent approximation is often obtained when 𝑉𝑖𝑙 is assumed constant at the value for
saturated liquid. In this case,
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
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
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:-
x1d𝜇1 +x2d𝜇2 =0
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
𝑑𝑓̂1 𝑑𝑓̂2
𝑑𝑥1 𝑑𝑥2
lim 𝑓̂1
= lim 𝑓̂2
𝑥1→1 𝑥2→0
𝑥1 𝑥2
2⌋ 𝑑𝑓̂
1 𝑑𝑓̂̂̂1 𝑑𝑥2 𝑥2=0
⌋
𝑓̂̂1 𝑑𝑥1 𝑥1=1
= 𝑓̂
lim 2
𝑥 →0 𝑥2
2
𝑑𝑓̂̂̂1
⌋ =𝑓̂̂
𝑑𝑥1 𝑥1=1 1
𝑓̂̂̂2 𝑑𝑓̂̂̂2
lim = ⌋𝑥
𝑥2→0 2 𝑑𝑥2 2=0
𝑥
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,
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
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;
For n-heptane;
This Told value is used as our initial guess value for the iterative process in calculation of
Bubble point T.
now,
Psat1, new = P/ ( x1 + x2 ( PSat2, old / PSat1, old)) [here, we have assumed ideal mixture, which
implies ℽi=1]
Therefore,
= 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,
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.
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
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.
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.
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)
∑Ziki /(1+ν(ki-1)) =1
now xi=yi/ki
x1= 0.2859, x2 =0.3810, x3= 0.3331
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
𝑑𝑓̂1 𝑑𝑓̂2
𝑑𝑥1 𝑑𝑥2
lim 𝑓̂1 = lim 𝑓̂2
𝑥1→1 𝑥2→0
𝑥1 𝑥2
𝑑𝑓̂̂̂1
⌋ =𝑓̂̂
𝑑𝑥1 𝑥1=1 1
Now by RHS=1, we get
𝑓̂̂̂2 𝑑𝑓̂̂̂2
lim = ⌋𝑥
𝑥2→0 𝑥2 𝑑𝑥2 2=0
MeOH-H2O system
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
= 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
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
= 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.
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
/
𝝏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 .