Calculating the boiling temperature

Click For Summary

Homework Help Overview

The problem involves calculating the boiling temperature of a liquid when the pressure is increased from 800 mmHg to 810 mmHg. The context is rooted in thermodynamics, specifically utilizing Clapeyron's equation to relate changes in pressure and temperature during phase transitions.

Discussion Character

  • Exploratory, Conceptual clarification, Mathematical reasoning, Assumption checking

Approaches and Questions Raised

  • The original poster attempts to apply Clapeyron's equation but expresses uncertainty regarding the volume differences between phases and the constancy of the heat of vaporization. They explore the implications of assuming constant values for these parameters and question the correctness of their assumptions.
  • Some participants affirm the original poster's approach, discussing the validity of neglecting the volume of the liquid and substituting the ideal gas law. They reference the derivation of the Clausius-Clapeyron equation and suggest that the heat of vaporization can be treated as constant over small intervals.
  • Others propose alternative forms of the equations, discussing the integration of the Clausius-Clapeyron equation and the implications of approximating differentials.

Discussion Status

The discussion is active, with participants providing insights and affirmations regarding the original poster's analysis. There is a focus on clarifying the assumptions made in applying the equations, and while various interpretations and approaches are explored, there is no explicit consensus on the final result or methodology.

Contextual Notes

Participants note the lack of information regarding the change in entropy at the new pressure and the implications of assuming constant heat of vaporization. The discussion also highlights the challenges of applying differential approximations in the context of the problem.

fluidistic
Gold Member
Messages
3,932
Reaction score
283

Homework Statement


I'm stuck on the following problem: A particular liquid boils at 127°C at a pressure of 800 mmHg. It has a heat of vaporization of 1000 cal/mole. At what temperature will it boil if the pressure is raised to 810 mmHg?

Homework Equations


Clapeyron's equation: ##\frac{dP}{dT}=\frac{l}{T\Delta v}##. (1)
##l=T\Delta s##. (2)

The Attempt at a Solution


Since the problem is given right after introducing the Clapeyron's equation in the book, I guess I must use it. However nothing is said about the difference in volumes of the gaseous and liquid phase of the substance.
Some thoughts: Since the pressure difference is small, I guess I can consider the heat of vaporization ##l## as a constant for the problem.
So I could calculate the change in entropy of the substance when it boils at 127°C and pressure of 800 mmHg. But I don't see how this would help me to calculate the temperature I'm asked to find. I'd need to know the change in entropy (which I know is lower than the one at pressure of 800 mmHg) of the substance if it boils when the pressure is 810 mmHg.

Second thoughts. If I consider that ##\frac{dP}{dT}## is a constant between T=127°C and the temperature I'm looking for, then ##T\Delta v## is also constant (applying Clapeyron's equation as well as assuming ##l## constant). Now, ##\Delta v \approx v^\text{gas}## because 1 mole of gas occupies a somewhat much greater volume than 1 mole of liquid. So ##Tv^\text{gas}=\text{constant}##. If I assume that the gas is ideal, then ##v=\frac{RT}{P}##. Thus ##\frac{T^2R}{P}=\text{constant} \Rightarrow \frac{T^2}{P}=\text{constant}##.
A simple plugging and chugging and isolating ##T^2## leads me to ##T\approx 129.5°C##.
It looks like I've solved the problem when writting it up here. I wonder if my assumptions are correct (that the heat of vaporization as well as dP/dT are constants in the region where I'm interested) and if I've reached the correct result.
Thank you for your time and effort.Edit: I doubt my answer is right since I've never used the value of ##l=1000 cal/mol##. I considered it constant, that all I did about it.
 
Last edited:
Physics news on Phys.org
You did a very nice job of analyzing this. You were very perceptive to substitute the ideal gas law and neglect the volume of the liquid. This is exactly what Clausius did when he derived the Clausius-Clapeyron equation:
\frac{dP}{dT}=\frac{lP}{RT^2}
Rearranging:
\frac{dlnP}{d(1/T)}=-\frac{l}{R}

Since the change in lnP and the change in 1/T are going to be very small, you can assume that, over that small an interval, l is nearly constant. So,

\frac{ΔlnP}{Δ(1/T)}=-\frac{l}{R}
 
Chestermiller said:
You did a very nice job of analyzing this. You were very perceptive to substitute the ideal gas law and neglect the volume of the liquid. This is exactly what Clausius did when he derived the Clausius-Clapeyron equation:
\frac{dP}{dT}=\frac{lP}{RT^2}

Perhaps a bit more straightforwardly:

Δp/ΔT = lp/RT2 or
ΔT = RT2Δp/lp.
Right? Those differentials give me headaches ... :smile:
 
Last edited:
rude man said:
Perhaps a bit more straightforwardly:

Δp/ΔT = lp/RT2 or
ΔT = RT2Δp/lp.
Right? Those differentials give me headaches ... :smile:

Yes. But one of the nice features of the Clausius-Clapeyron equation is that the heat of vaporization is a relatively weak function of temperature, so that the integrated version (assuming constant l) typically applies quite accurately over fairly large changes in temperature and pressure (i.e., several tens of degrees):

\ln(P_2/P_1)=\frac{l(T_2-T_1)}{RT_2T_1}
 
Chestermiller said:
Yes. But one of the nice features of the Clausius-Clapeyron equation is that the heat of vaporization is a relatively weak function of temperature, so that the integrated version (assuming constant l) typically applies quite accurately over fairly large changes in temperature and pressure (i.e., several tens of degrees):

\ln(P_2/P_1)=\frac{l(T_2-T_1)}{RT_2T_1}

I think the math's the same:

Δp/ΔT = lp/RT2 or more accurately
dp/dT = lp/RT2
dp/p = l/RT2 dT
integrating from p1 to p2 on the LHS and T1 to T2 on the RHS gives

ln(p2/p1) = (-l/R)(1/T2 - 1/T1).

EDIT: never mind Chet, I approximated dp/dT as Δp/ΔT which is not as accurate as dp/dT integrated as per your result. Not a big difference in the answer but still I should have integrated.


Interesting what you pointed out about Clapeyron first publishing his relation assuming ideal gases ... Fermi managed two independent means of deriving the more general dp/dT = l/TΔv. Of course, that was in the 1930's ...
 
Last edited:

Similar threads

  • · Replies 5 ·
Replies
5
Views
3K
Replies
12
Views
3K
  • · Replies 23 ·
Replies
23
Views
2K
  • · Replies 1 ·
Replies
1
Views
2K
Replies
4
Views
2K
Replies
2
Views
3K
Replies
30
Views
5K
Replies
1
Views
2K
  • · Replies 1 ·
Replies
1
Views
2K
  • · Replies 1 ·
Replies
1
Views
2K