UV-Vis spectroscopy: Changes in refractive index

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Discussion Overview

The discussion revolves around the control of changes in refractive index when obtaining UV-Vis spectra of aqueous solutions using a double beam spectrometer. Participants explore how these changes occur, their implications for absorbance measurements, and the calculations involved in understanding reflectivity in this context.

Discussion Character

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

Main Points Raised

  • One participant inquires about whether the spectrometer automatically accounts for changes in refractive index or if manual adjustments are necessary.
  • Several participants discuss the angle at which the beam hits the surface of the liquid, with a consensus that it is perpendicular, which affects refraction and reflection.
  • There is a mathematical expression provided for reflection based on refractive indices, indicating that changes in refractive index will influence reflection but not refraction when the beam is perpendicular.
  • A participant questions whether changes in reflection due to refractive index will affect absorbance measurements.
  • Another participant suggests performing a reflectivity calculation to understand the impact of dissolved samples on refractive index and reflectivity, emphasizing the importance of independent calculations for comprehension.
  • Some participants express frustration over the expectation of simple yes or no answers, advocating for deeper understanding through calculations.
  • One participant notes that the effect of changes in refractive index on absorbance is "negligibly small," but this is not universally agreed upon.

Areas of Agreement / Disagreement

Participants express differing views on the necessity of calculations to understand the effects of refractive index changes, with some advocating for deeper exploration while others seek straightforward answers. The discussion remains unresolved regarding the extent to which refractive index changes impact absorbance measurements.

Contextual Notes

Participants mention the need to consider multiple reflections and the specific refractive indices of air, water, and the cuvette material, indicating that assumptions and definitions play a significant role in their calculations and conclusions.

Ella98
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I wanted to know how do you control for changes in refractive index when you get the UV-Vis spectrum of an aqueous solution in a double beam spectrometer? Is that something the equipment does automatically? Or something I have to do? Also, how do these changes in refractive index occur? Thanks for any help you can provide.
 
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How does the beam hit the surface of the liquid? At what angle?
 
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Borek said:
How does the beam hit the surface of the liquid? At what angle?
The beam is perpendicular to the surface of the cuvette holding the liquid. Thanks!
 
Ella98 said:
The beam is perpendicular to the surface of the cuvette holding the liquid. Thanks!
It is not going to refract if the incident beam is perpendicular to the surface. Changes in refractive index will change the reflection though.
R=\left |\frac{n_{1}-n_{2}}{n_{1}+n_{2}} \right |^{2}
 
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HAYAO said:
It is not going to refract if the incident beam is perpendicular to the surface. Changes in refractive index will change the reflection though.
R=\left |\frac{n_{1}-n_{2}}{n_{1}+n_{2}} \right |^{2}
Will changes in reflection affect my absorbance measurements? I just want to know if the changes in refractive index will affect my absorbance measurements. Thanks, Hayao.
 
It might be nice if you could attempt a reflectivity calculation on your own of the case where there is only water in the cuvette, and then think about how much that changes when there is a sample dissolved in it. Don't ask for "do it for me". Try your own attempt and we'll guide you.To start you off, look up refractive index for air, water, and cuvette (most likely made of quartz). And then put the numbers in the Frensel reflectivity equation above for both intersection, namely air-quartz and quartz-water. At this point, you will have to make an assumption based on these numbers whether you can neglect multiple reflection (reflection of a reflection of a reflection of a...) or not. Then calculate how much of the initial light passes through the cuvette with water. (Note: we have four intersection in total, i.e. two quartz walls.)

If you have done that, then make a reasonable estimate of how much the refractive index of the water changes when you have something dissolved in it. Contemplate how much that would affect the reflectivity.
 
HAYAO said:
It might be nice if you could attempt a reflectivity calculation on your own of the case where there is only water in the cuvette, and then think about how much that changes when there is a sample dissolved in it. Don't ask for "do it for me". Try your own attempt and we'll guide you.To start you off, look up refractive index for air, water, and cuvette (most likely made of quartz). And then put the numbers in the Frensel reflectivity equation above for both intersection, namely air-quartz and quartz-water. At this point, you will have to make an assumption based on these numbers whether you can neglect multiple reflection (reflection of a reflection of a reflection of a...) or not. Then calculate how much of the initial light passes through the cuvette with water. (Note: we have four intersection in total, i.e. two quartz walls.)

If you have done that, then make a reasonable estimate of how much the refractive index of the water changes when you have something dissolved in it. Contemplate how much that would affect the reflectivity.

I'm sorry I didn't mean with my reply to imply I wanted you to do any calculations for me. I just thought what I asked was a yes or no question. I didn't know calculations will be required to answer it. Thanks for the help! I really appreciate it.
 
Ella98 said:
I'm sorry I didn't mean with my reply to imply I wanted you to do any calculations for me. I just thought what I asked was a yes or no question. I didn't know calculations will be required to answer it. Thanks for the help! I really appreciate it.
And that's not what I meant, neither.

You can't understand something with simple yes or no. You understand it by really doing the calculations on your own, even if you intuitively understand why. I wanted you to really understand it. What if you had to teach someone how to use UV-Vis absorption spectrometer and you were asked the same question? Yes or no isn't always the answer that they are looking for.The answer is it's negligibly small enough, btw.
 

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