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Chemical and Biochemical Engineering

Thermodynamics
CHEN 30030

Assignment 2

Estimation of Solubility and Henry’s Law Constant of CO2 and N2 in Toluene


and Methanol

Nalin Seth
14203218
Problem Statement:
1. Estimate the solubility and Henry’s Law constants of both CO2 (carbon dioxide) and N2 (nitrogen) in
the binary liquid mixture as a function of the mole fraction of one of the species of the binary pair (at
25oC and 1.013 bar).
2. Where possible, compare the Henry’s Law constants for the pure components with experiment. Discuss
your results.

Solution: Carbon-di-Oxide
Binary System: Toluene and Methanol
Since the partial pressure of carbon dioxide and the vapour pressure of Toluene and Methanol are low, total pressure must
be low, and we can assume that

f/P=1
𝑽𝒍𝑪𝑶𝟐 (𝑷−𝟏.𝟎𝟏𝟑𝒃𝒂𝒓)
exp ( )= 1
𝑹𝑻
Using the regular solution model for γ, we obtain:
𝒚𝑪𝑶𝟐 .𝑷
xCO2= 𝑽𝑳 (𝜹𝑪𝑶𝟐−𝜹)^𝟐
𝒇𝑳𝑪𝑶𝟐 (𝑻,𝑷=𝟏.𝟎𝟏𝟑 𝒃𝒂𝒓) 𝒆𝒙𝒑( 𝑪𝑶𝟐 )
𝑹𝑻

with δ= Σ φj* δj
𝑓𝑙
The reduced temperature of CO2 is Tr = 298.15K/304.3K=0.98 so from Shair Prausnitz co-relation 𝑃𝐶
= 0.60. Hence

𝑓 𝑙 = 0.60 ∗ 73.76 𝑏𝑎𝑟 = 𝟒𝟒. 𝟐𝟔 𝒃𝒂𝒓.


To calculate the activity coefficients, we will assume that CO2 is only slightly soluble in the solvents, therefore its
volume fraction is small, we will verify this assumption.

Thus, as a first guess, the contribution of CO2 to δ will be neglected.

To compute the solubility of CO2 in pure toluene/methanol, we note that from Liquid-Volume and Solubility
parameters (J.M> Prausnitz & F.H. Shair AIChE (1961).

Gas/ Solvent VL (cc/mole) Δ (Cal/cc)^2


Toluene 107 8.9
Methanol 40.04 14.28
Carbon dioxide 55 6.0

For toluene:

δ = δT = 8.9 cal/cc and (𝜹𝑪𝑶𝟐 − 𝜹)^𝟐= 8.4 cal/cc = 35.15 J/cc

𝟏.𝟎𝟏𝟑 𝒃𝒂𝒓
xCO2= 𝟓𝟓∗𝟑𝟓.𝟏𝟓 = 1.05* 10^-2
𝟒𝟒.𝟐𝟔 𝒃𝒂𝒓∗ 𝒆𝒙𝒑( )
𝟖.𝟑𝟏𝟒∗𝟐𝟗𝟖.𝟏𝟓

H= P/ xCO2= 1.013bar/1.05*10^-2= 96.47 bar/mole fraction


For Methanol:

δ = δM = 14.28 cal/cc and (𝜹𝑪𝑶𝟐 − 𝜹)^𝟐= 68.55 cal/cc = 286.88 J/cc

𝟏.𝟎𝟏𝟑 𝒃𝒂𝒓
xCO2= 𝟓𝟓∗𝟐𝟖𝟔.𝟖𝟖 = 1.322*10^-3
𝟒𝟒.𝟐𝟔 𝒃𝒂𝒓∗ 𝒆𝒙𝒑( )
𝟖.𝟑𝟏𝟒∗𝟐𝟗𝟖.𝟏𝟓

H= P/ xCO2= 1.013bar/1.322*10^-3 = 25749.98 bar/mole fraction


Finally, the solubility of CO2 in a 50 mole % toluene and 50 mole % methanol mixtures are found.
𝐋
𝐕𝐦𝐢𝐱 = 𝐱𝐓 𝐕𝐓𝐥 + 𝐱𝐌 𝐕𝐌𝐥
= 0.5*107 + 0.5*40.04
= 73.52 cc/mole

φT= (0.5*107)/73.52= 0.727 φM=(0.5*40.4)/73.52


δ= 0.727*8.9+0.274*14.28= 10.3938 cal/cc^0.5
(𝜹𝑪𝑶𝟐 − 𝜹)^𝟐= 19.305 cal/cc
=80.79 J/cc
𝟏.𝟎𝟏𝟑 𝒃𝒂𝒓
xCO2= 𝟓𝟓∗𝟖𝟎.𝟕𝟗 =4.69* 10^-3
𝟒𝟒.𝟐𝟔 𝒃𝒂𝒓∗ 𝒆𝒙𝒑( )
𝟖.𝟑𝟏𝟒∗𝟐𝟗𝟖.𝟏𝟓

H= P/ xCO2= 215.66 bar/mole fraction.

For CO2 in Toluene/Methanol

Solution: Nitrogen
Since the partial pressure of nitrogen and the vapour pressure of Toluene and Methanol are low, total pressure must be low,
and we can assume that

f/P=1
𝑽𝒍𝑵𝟐 (𝑷−𝟏.𝟎𝟏𝟑𝒃𝒂𝒓)
exp ( )= 1
𝑹𝑻
Using the regular solution model for γ, we obtain:
𝒚𝑵𝟐 .𝑷
xN2= 𝑽𝑳 (𝜹𝑵𝟐−𝜹)^𝟐
𝒇𝑳𝑵𝟐 (𝑻,𝑷=𝟏.𝟎𝟏𝟑 𝒃𝒂𝒓) 𝒆𝒙𝒑( 𝑵𝟐 )
𝑹𝑻

with δ= Σ φj* δj
𝑓𝑙
The reduced temperature of N2 is Tr = 298.15K/126.2K=2.36 so from Shair Prausnitz co-relation 𝑃𝐶
= 1011.52.

Hence 𝑓 𝑙 = 1011.52 ∗ 33.94 𝑏𝑎𝑟 = 𝟑𝟒𝟑𝟑𝟎. 𝟗𝟖𝟖 𝒃𝒂𝒓.


To calculate the activity coefficients, we will assume that N2 is only slightly soluble in the solvents, therefore its
volume fraction is small, we will verify this assumption.

Thus, as a first guess, the contribution of N2 to δ will be neglected.

To compute the solubility of CO2 in pure toluene/methanol, we note that from Liquid-Volume and Solubility
parameters (J.M> Prausnitz & F.H. Shair AIChE (1961).

Gas/ Solvent VL (cc/mole) Δ (Cal/cc)^2

Toluene 107 8.9

Methanol 40.04 14.28

Nitrogen 32.4 2.58

For toluene:

δ = δT = 8.9 cal/cc and (𝜹𝑵𝟐 − 𝜹)^𝟐= 39.94 cal/cc = 167.15 J/cc

𝟏.𝟎𝟏𝟑 𝒃𝒂𝒓
xN2= 𝟑𝟐.𝟒∗𝟏𝟔𝟕.𝟏𝟓 = 3.35*10^-03
𝟑𝟑.𝟗𝟒 𝒃𝒂𝒓∗ 𝒆𝒙𝒑( )
𝟖.𝟑𝟏𝟒∗𝟐𝟗𝟖.𝟏𝟓

H= P/ xN2= 1.013bar/3.35*10^-3= 301.715 bar/mole fraction

For Methanol:

δ = δM = 14.28 cal/cc and (𝜹𝑵𝟐 − 𝜹)^𝟐= 130.64 cal/cc = 572.88 J/cc

𝟏.𝟎𝟏𝟑 𝒃𝒂𝒓
xN2= 𝟑𝟐.𝟒∗𝟓𝟕𝟐.𝟖𝟖 = 1.67*10^-5
𝟑𝟑.𝟗𝟒 𝒃𝒂𝒓∗ 𝒆𝒙𝒑( )
𝟖.𝟑𝟏𝟒∗𝟐𝟗𝟖.𝟏𝟓

H= P/ xN2= 1.013bar/1.67*10^-5 = 60634.58 bar/mole fraction


Finally, the solubility of CO2 in a 50 mole % toluene and 50 mole % methanol mixtures are found.
𝐋
𝐕𝐦𝐢𝐱 = 𝐱𝐓 𝐕𝐓𝐥 + 𝐱𝐌 𝐕𝐌𝐥
= 0.5*107 + 0.5*40.04
= 73.52 cc/mole

φT= (0.5*107)/73.52= 0.727 φM= (0.5*40.4)/73.52


δ= 0.727*8.9+0.274*14.28= 10.3938 cal/cc^0.5
(𝜹𝑵𝟐 − 𝜹)^𝟐= 61.055 cal/cc
=255.517 J/cc
𝟏.𝟎𝟏𝟑 𝒃𝒂𝒓
xCO2= 𝟑𝟐.𝟒∗𝟐𝟓𝟓.𝟓𝟏𝟕 =1.05* 10^-3
𝟑𝟑.𝟗𝟒 𝒃𝒂𝒓∗ 𝒆𝒙𝒑( )
𝟖.𝟑𝟏𝟒∗𝟐𝟗𝟖.𝟏𝟓

H= P/ xN2= 934.32 bar/mole fraction.

For N2 in Toluene/Methanol

As the experimental data for Carbon di oxide is not available for toluene the data for CO2 in water is presented below

Henry's Constant for Carbon Dioxide in Water - from Carroll et al.

Due to lack of solubility data for CO2 and N2 in given binary systems of toluene and Methanol. The comparison of
experimental Henry law constant is not possible. Further research on the data is required for a comparison. We
know the Henry law constant for CO2 in water at 25 C is 3.3*10^-2 mol/L.atm and for N2 6.1*10^-4 which is well
below to that of Toluene and Methanol. This proves that CO2 and N2 can easily be absorbed in the given mixture.