Spectrophotometry of chromate-dichromate equilibrium

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Discussion Overview

The discussion focuses on the application of spectrophotometry to analyze the chromate-dichromate equilibrium, specifically aiming to determine the relative concentrations of chromate and dichromate ions in a mixture. Participants explore the methodology for measuring absorbance at various wavelengths and the implications of the Beer-Lambert law in this context.

Discussion Character

  • Technical explanation
  • Mathematical reasoning
  • Debate/contested

Main Points Raised

  • One participant suggests that to determine the concentration of colored ions, absorbance/transmittance must be measured at multiple wavelengths, but is uncertain about the subsequent steps.
  • Another participant counters that typically, one should select a single wavelength where absorbance is highest for better sensitivity, referencing the Beer-Lambert law.
  • A later reply reiterates the importance of selecting a wavelength with the highest absorbance and proposes a method for calculating the concentrations of two ions in a mixture using total absorbance equations.
  • Participants discuss the need for a second wavelength measurement to create a system of equations for solving the concentrations of the two ions, emphasizing the importance of selecting wavelengths that maximize the difference in absorptivity ratios.

Areas of Agreement / Disagreement

There is no consensus on the initial approach to measuring absorbance, with differing opinions on whether multiple wavelengths or a single wavelength should be used. Participants agree on the need for a second measurement to solve for concentrations, but the method of selection for wavelengths remains contested.

Contextual Notes

Participants express uncertainty about the specific steps following the measurement of absorbance and the implications of their chosen methodology. There are also unresolved questions regarding the optimal wavelength selection and the mathematical relationships involved in the analysis.

24forChromium
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The goal is to determine the relative abundance of the ions using the spectrophotometer. As far as I understand, to determine the relative (or absolute) concentration of a coloured ion in solution, one must have the absorbance/transmittance of the solution at multiple wavelengths.

Once the absorbance/transmittance of a solution over various wavelengths of light is acquired, one should do something with the maximum point of the absorbance/transmittance over frequency graph, which I do not know.

Please explain the following steps, point out any mistakes in my procedure and suggest a wavelength range to examine the chromate-dichromate mixture in.
 
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24forChromium said:
As far as I understand, to determine the relative (or absolute) concentration of a coloured ion in solution, one must have the absorbance/transmittance of the solution at multiple wavelengths.

No, you select one wavelength for that. Typically we will select the one where absorbance is the highest, as it gives you the highest sensitivity (you can measure lower concentrations).

Google Beer-Lambert law.
 
Borek said:
No, you select one wavelength for that. Typically we will select the one where absorbance is the highest, as it gives you the highest sensitivity (you can measure lower concentrations).

Google Beer-Lambert law.
Thanks for the reply, so what happens is that, across a certain length of the liquid, the solution will absorb an amount of light that is related to its concentration. Is there a way to find out how much of each ion there is if there is a mixture of two liquids?

Here is what I think: first decide on a certain wavelength, find the total absorbance of the mixture (A_total)

A_total = A_1 + A_2 where A_1 and A_2 represent the absorbance of each chemical at this wavelength
A_total = a_1 * L * C_1 + a_2 * L * C_2 where a represent the absorptivity of each chemical, L is the length of the examined liquid, C represent the concentration of each solute.

Is that right?
 
OK so far. Now, if you select another wavelength you will have another measurement result. That will yield second equation in the same two unknowns (c1 and c2).

You just have to select such pair of wavelengths that a1/a2 ratios are as different as possible (that will help minimalize errors).
 

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