Spectrophotometry area of chemistry

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Discussion Overview

The discussion revolves around the application of spectrophotometry in determining equilibrium constants in a chemical reaction involving gold bromide complexes. Participants explore the use of Beer’s law and the calculation of concentrations based on absorbance measurements in a laboratory setting.

Discussion Character

  • Technical explanation
  • Mathematical reasoning
  • Homework-related

Main Points Raised

  • One participant expresses a lack of familiarity with spectrophotometry and seeks assistance with calculations related to equilibrium concentrations and constants.
  • Another participant applies Beer’s law to calculate the extinction coefficient for AuBr_{4}^{-} using absorbance data from a separate experiment.
  • A third participant suggests using compound-specific extinction coefficients and notes that AuBr_{2}^{-} does not absorb at 382 nm, implying its extinction coefficient is zero.
  • There is a discussion about using the extinction coefficient derived from the second experiment to find the concentration of AuBr_{4}^{-} in the first experiment.

Areas of Agreement / Disagreement

Participants present different approaches to the calculations, and while some agree on the use of Beer’s law, there is no consensus on the specific methods or assumptions regarding the extinction coefficients.

Contextual Notes

Participants mention the need for compound-specific extinction coefficients and the implications of certain species not absorbing at the measurement wavelength, which may affect calculations.

Who May Find This Useful

Students and researchers interested in spectrophotometry, chemical equilibria, and the application of Beer’s law in analytical chemistry may find this discussion relevant.

thenewbosco
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I am not familiar with this area of chemistry. The theory given in the manual doesn't really help. The only thing it says is that absorption is proportional to concentration. Maybe you can give me some assistance on how to get started and some equations that i can use.

The eqilibrium constant for: [tex]AuBr_{4}^{-} + 2Au + 2Br^{-} --> 3AuBr_{2}^{-}[/tex] can be determined by preparing a solution of AuBr[tex]_{4}^{-}[/tex] and AuBr[tex]_{2}^{-}[/tex] in contact with a piece of gold metal.
In one experiment a solution initially containing [tex]6.41x10^{-4}[/tex] mol/L of dissolved gold (both AuBr[tex]_{4}^{-}[/tex] and AuBr[tex]_{2}^{-}[/tex]) in 0.4 M HBr was allowed to attain equilibrium in the presence of gold metal. The absorbance was 0.445 in a 1.00 cm cell at 382nm.

In a separate experiment, the absorbance of a [tex]8.54x10^{-5}[/tex]M solution of only AuBr[tex]_{4}^{-}[/tex] (no AuBr[tex]_{2}^{-}[/tex] ) in 0.4 M HBr was determined in a 1.00cm cell to be 0.410 at 382nm. (AuBr[tex]_{2}^{-}[/tex] does not absorb at 382nm.)

a) calculate the equilibrium concentrations and b) evaluate the equilibrium constant.

I can get b) if i knew how to do a) can someone help me with this one?


Thanks
 
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here is what i have done can someone tell me if it is correct:

Given that [tex]A={\epsilon}cl[/tex] (from beers law i found on the internet)

I can use this and experiment two to get the [tex]{\epsilon} = 0.410/8.54^{-5}=4800.94[/tex]

Now from this value of epsilon, can i use it with beer's law again to calculate the concentration of AuBr[tex]_{4}^{-}[/tex] in the first experiment with the new A value (.445)?

Then i would have a concentration for AuBr[tex]_{4}^{-}[/tex] and i can subtract it from the combined concentration of 6.41E-4 M, to get [AuBr2].

Is this correct?

thanks
 
You should use compound-specific extinction coefficients, I mean, [itex]\displaystyle \epsilon_{{AuCl_4}^-}[/itex] and [itex]\displaystyle \epsilon_{{AuCl_2}^-}[/itex]

However, it was said that the latter species does not absorb at 382 nm, which means that the extinction coefficient for [AuBr2]- will be zero.

The second separate experiment will allow you to know the extinction coefficient for the first species, namely, [AuBr4]-. In the first experiment, you can find the final concentration of this species after equilbrium has been reached. The difference will totally be from the second Au+-bearing species, as solid Au is not spectrometrically specific.
 
wow thanks
i got that exact same question on my lab manual too! :P
 

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