Natural Log of Units: What Happens to the Units?

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Homework Help Overview

The discussion revolves around the implications of taking the natural logarithm of quantities with units, specifically focusing on vapor pressure in kPa and its application in thermodynamic equations involving Gibbs free energy and equilibrium constants.

Discussion Character

  • Conceptual clarification, Assumption checking, Mixed

Approaches and Questions Raised

  • Participants explore the validity of taking the natural logarithm of quantities with units, questioning what happens to the units in such cases. There is a discussion about the implications of using logarithmic differences and the necessity for dimensionless quantities.

Discussion Status

The conversation includes various perspectives on the treatment of units in logarithmic expressions. Some participants suggest that while taking logs of dimensioned quantities is problematic, differences of logs can yield meaningful results. Others express confusion regarding the treatment of units in specific thermodynamic contexts.

Contextual Notes

There are references to specific equations and constants, such as the gas constant and molarity, which are central to the discussion but may not be fully resolved. The conversation reflects a mix of established principles and ongoing uncertainties regarding dimensional analysis in logarithmic calculations.

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Homework Statement


We're doing a lab and we basically had to find ln(Pv), where Pv is vapor pressure of isopropanol. Well, the pressure is initially measured in kPa, but what happens to the units if you take a natural log of that whole thing?
For example, if I take ln(5 kPa), do the units remain or disappear, or what happens to them? It'd be really nice if they disappeared :) But I'm doubting that possibility

Thanks
 
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This is a really common abuse. You should technically only take the log of a dimensionless quantity. But in your problem you are only considering differences of logs. So e.g. ln(5 kPa)-ln(3 kPa)=(ln(5)+ln(kPa))-(ln(3)+ln(kPa))=ln(5)-ln(3). The expression ln(kPa) is complete nonsense. Luckily, the nonsense cancels.
 
Thanks! We used it in slope calculations and they were subtracted and I carried the ln(kPa) through the whole calculation only to realize that in the next step I'd have to do something with them. Thanks again :) Now I can finish my write-up.
 
I'm confused. Let's look at the thermodynamic relationship \DeltaG=-RTlnKeq. In UV thermal melting of non-self complementary DNA duplexes this is defined as Keq=\frac{2(1-\Theta)}{\Theta^{2}Ct} where \Theta is the fraction of broken basepairs observed experimentally and Ct is the concentration of the duplex (Molarity). The gas constant has units of Joules*Mol^{-1} *K^{-1}, and the temperature is obviously is Kelvin to cancel out. In these cases the calculated \DeltaG is reported in Joules*Mol^{-1}. What happened to the unit of molarity from the concentration term from the equilibrium constant?
 
ytty said:
I'm confused. Let's look at the thermodynamic relationship \DeltaG=-RTlnKeq. In UV thermal melting of non-self complementary DNA duplexes this is defined as Keq=\frac{2(1-\Theta)}{\Theta^{2}Ct} where \Theta is the fraction of broken basepairs observed experimentally and Ct is the concentration of the duplex (Molarity). The gas constant has units of Joules*Mol^{-1} *K^{-1}, and the temperature is obviously is Kelvin to cancel out. In these cases the calculated \DeltaG is reported in Joules*Mol^{-1}. What happened to the unit of molarity from the concentration term from the equilibrium constant?

ln is always unitless, so there shouldn't be any unit of molarity.

I think the confusion arises from the fact that, intuitively, it doesn't make sense to take the log of a non-dimensionless quantity, because the ln of a quantity depends on what units you choose. And indeed, this is the case: -RTlnKeq is physically meaningless. Fortunately, whenever we need to calculate an actual physical quantity--for example, the change in Gibbs free energy from a given reaction--we subtract one standard delta_G from another and get -RT*ln(Keq1/Keq2). Keq1/Keq2 is now a dimensionless quantity, and the log of it makes physical sense.
 
Same answer as before. If you only care about differences of the quantity, then log(a)-log(b)=log(a/b). Whatever units are in the argument of the log will cancel out.
 
This is not a correct definition of Keq. Keq equals equilibrium value of reaction quotient, reaction quotient is built using not concentrations but activities - and activities are dimensionless. Definition you are using is a simplified one, derived from the full one - and it nonchalantly ignores exact approach.
 

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