Calculate the boiling temperature of methanol from thermodynamic data

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Discussion Overview

The discussion revolves around calculating the boiling temperature of methanol at 60 atm using thermodynamic data, including critical temperature, critical pressure, and acentric factor. Participants explore various methods and equations, such as the Pitzer Correlation, Clausius equation, and Clausius-Clapeyron equation, while addressing the need for additional data like enthalpy of vaporization.

Discussion Character

  • Exploratory, Technical explanation, Debate/contested, Mathematical reasoning

Main Points Raised

  • One participant suggests using the Pitzer Correlation to calculate the fugacity coefficient but notes the lack of temperature data.
  • Another participant provides the definition of the acentric factor and questions how to apply it to find the reduced pressure.
  • Several participants discuss the calculation of reduced pressure and temperature, with one calculating a reduced pressure of 0.0277 and corresponding pressure of 2.16 atm.
  • There is a suggestion to use the Clausius-Clapeyron equation to find the boiling temperature at 60 atm, but participants express uncertainty due to missing enthalpy data.
  • One participant explains that the logarithm of vapor pressure is approximately linear in the reciprocal of absolute temperature, proposing to interpolate between known points to find the boiling temperature.
  • Another participant shares their derived linear equation for lnP vs 1/T and seeks clarification on their calculations, expressing confusion over a high negative number obtained for 1/T.
  • Participants calculate the slope of the line and formulate an equation for lnP, discussing how to find the temperature corresponding to a pressure of 60 atm.
  • Expressions of enthusiasm for learning and collaboration are noted, with participants encouraging each other throughout the discussion.

Areas of Agreement / Disagreement

Participants generally agree on the methods to approach the problem, but there are uncertainties regarding the application of formulas and the need for additional data. The discussion remains unresolved as participants continue to seek clarification and assistance.

Contextual Notes

Participants express limitations due to missing data, such as enthalpy of vaporization, and the dependency on definitions and assumptions related to the acentric factor and reduced properties.

Who May Find This Useful

Students and professionals interested in thermodynamics, particularly those working with phase equilibria and vapor-liquid calculations, may find this discussion beneficial.

il postino
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Homework Statement
Calculate the boiling temperature of methanol at 60 atm knowing that Tc = 513K, Pc = 78atm and the acentricity is W.
Relevant Equations
Pitzer correlation?
Clausius equation?
Calculate the boiling temperature of methanol at 60 atm knowing that Tc = 513K, Pc = 78 atm and the acentricity is 0.555.

I would like you to help me start the exercise.
I thought about using the Pitzer Correlation to be able to calculate the fugacity coefficient, but I don't have the Temperature.
I thought about using, then, the Clausius equation but I don't have the enthalpy either.
I don't know how to start.
Thank you very much!
 
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The acentric factor is defined by the equation $$\omega=-1-\log{(P_r^{sat})_{T_r=0.7}}$$What value does this give you for ##(P_r^{sat})_{T_r=0.7}##?
 
Last edited:
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Chestermiller said:
The acentric factor is defined by the equation $$\omega=-1-\log{(P_r^{sat})_{T_r=0.7}}$$What value does this give you for ##(P_r^{sat})_{T_r=0.7}##?
Hi! Thank you very much for answering!
I have not been taught this formula.
How can I apply it to solve the exercise?
 
Last edited by a moderator:
il postino said:
Hi! Thank you very much for answering!
I have not been taught this formula.
How can I apply it to solve the exercise?
I'll help you. You can start by answering my question.
 
[QUOTE = "Chestermiller, publicación: 6368754, miembro: 345636"]
The acentric factor is defined by the equation $$\omega=-1-\log{(P_r^{sat})_{T_r=0.7}}$$What value does this give you for ##(P_r^{sat})_{T_r=0.7}##?
[/QUOTE]

But how do I get ##P_r^{sat}## to find ##w##?
excuse me
 
Last edited by a moderator:
il postino said:
But how do I get ##P_r^{sat}## to find ##w##?
excuse me
Sorry. ##\omega## is the acentricity. The spell checker changed acentricity to eccentricity and I didn't notice it.
 
Last edited:
Chestermiller said:
Sorry. ##\omega## is the acentricity. The spell checker changed acentricity to eccentricity and I didn't notice it.

Hi Chester!
I was investigating what you taught me.
With that formula I can get the reduced pressure:
##P_{r}=0.0277##

and knowing that ##P=P_{r} * P_c##
##P=2.16 atm##

On the other hand, I am considering that ##T_{r}=0.7##
Thus ##T=0.7*513K=359.1 K##
It is right?

If this is correct, you could use the Clausius Clapeyron equation to get the boiling temperature at 60 atm.
BUT I have no data on the enthalpy of vaporization.
What do you think?
Thank you very much!
 
il postino said:
Hi Chester!
I was investigating what you taught me.
With that formula I can get the reduced pressure:
##P_{r}=0.0277##

and knowing that ##P=P_{r} * P_c##
##P=2.16 atm##

On the other hand, I am considering that ##T_{r}=0.7##
Thus ##T=0.7*513K=359.1 K##
It is right?

If this is correct, you could use the Clausius Clapeyron equation to get the boiling temperature at 60 atm.
BUT I have no data on the enthalpy of vaporization.
What do you think?
Thank you very much!
You're on the right track. The development of the acentric factor is based on the fact that the the log of the vapor pressure of a pure fluid is approximately linear in the reciprocal of the absolute temperature. Smith and van Ness, introduction to Chemical Engineering Thermodynamics: "Since the logarithm of the vapor pressure of a pure fluid is approximately linear in the reciprocal of absolute temperature, we may write
$$\frac{d\log{P_r^{sat}}}{d(1/T_r)}=a$$where ##P_r^{sat}## is the reduced vapor pressure, ##T_r## is the reduced temperature, and a is the slope of the plot of ##\log{P_r^{sat}}## vs ##1/T_r##". If this is the case, then the natural log of the saturation pressure is also a linear function of the reciprocal of the absolute temperature. And you now have two points along this straight line: the critical point (78, 513) and (2.16, 359.1). So you can interpolate to get the temperature at 60 atm. (Incidentally, according to my calculator, at 0.7, the correct reduced pressure is 0.0279, and the corresponding pressure is 2.17 atm.)
 
Chestermiller said:
You're on the right track. The development of the acentric factor is based on the fact that the the log of the vapor pressure of a pure fluid is approximately linear in the reciprocal of the absolute temperature. Smith and van Ness, introduction to Chemical Engineering Thermodynamics: "Since the logarithm of the vapor pressure of a pure fluid is approximately linear in the reciprocal of absolute temperature, we may write
$$\frac{d\log{P_r^{sat}}}{d(1/T_r)}=a$$where ##P_r^{sat}## is the reduced vapor pressure, ##T_r## is the reduced temperature, and a is the slope of the plot of ##\log{P_r^{sat}}## vs ##1/T_r##". If this is the case, then the natural log of the saturation pressure is also a linear function of the reciprocal of the absolute temperature. And you now have two points along this straight line: the critical point (78, 513) and (2.16, 359.1). So you can interpolate to get the temperature at 60 atm. (Incidentally, according to my calculator, at 0.7, the correct reduced pressure is 0.0279, and the corresponding pressure is 2.17 atm.)

Then I am very happy! :bow:
Now I understand better with your explanation.
How can I continue?
 
  • #10
il postino said:
Then I am very happy! :bow:
Now I understand better with your explanation.
How can I continue?
Fit a straight line equation to lnP vs 1/T using the two points you already have, and then solve for the value of 1/T at which lnP=ln(60)
 
  • #11
Chestermiller said:
Fit a straight line equation to lnP vs 1/T using the two points you already have, and then solve for the value of 1/T at which lnP=ln(60)
Okey :) I will and inform you! Thank you!
 
  • #12
Chestermiller said:
Fit a straight line equation to lnP vs 1/T using the two points you already have, and then solve for the value of 1/T at which lnP=ln(60)

Hi Chester! you mean the 2 points ##(P; T)##:
##(2.144 ; 359.1)## and ##(78 ; 513)##

For these points, the linear equation is:

##y = -0,0002x + 0,003##

For ##ln (60)##, ##1/T## it gives me a very high and negative number.
What am I doing wrong?

Also, I know that the slope of that line should be:
##-ΔH_{v} /R##
 

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  • #13
The slope is $$m=\frac{\ln{78}-\ln{2.17}}{\left(\frac{1}{513}-\frac{1}{359.1}\right)}=-4288$$So the equation is $$\ln{p}=m\left(\frac{1}{T}\right)+b=-4288\left(\frac{1}{T}\right)+b$$So,
$$\ln{78}=-\frac{4288}{513}+b$$and$$b=12.72$$So,$$\ln{p}=-4288\left(\frac{1}{T}\right)+12.72$$So, at p=60, T=?
 
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  • #14
Chestermiller said:
The slope is $$m=\frac{\ln{78}-\ln{2.17}}{\left(\frac{1}{513}-\frac{1}{359.1}\right)}=-4288$$So the equation is $$\ln{p}=m\left(\frac{1}{T}\right)+b=-4288\left(\frac{1}{T}\right)+b$$So,
$$\ln{78}=-\frac{4288}{513}+b$$and$$b=12.72$$So,$$\ln{p}=-4288\left(\frac{1}{T}\right)+12.72$$So, at p=60, T=?

Thank you very much Chester!
You made me not only want to find the solution, but also LEARN more!
We will surely meet here!
Thank you very much!
Greetings from Argentina! :smile::smile:
 
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