GIGO Measurement of Lead Depends on Chemistry of

GIGO Measurement of Lead Depends on: Chemistry of Lead for Separations Chemistry of Lead for Creating a signal Chemistry of Lead for Creating Background Chemistry of Lead for the Stability of the Signal Garbage In = Garbage Out Sample Prep Instrument Out put Signal (Data)

Recall we mentioned that lead resides at surface of soils because of it’s insolubility

Beta

Recall from Quant Mass balance

Mass balance Make a definition to simplify the expression, and factor out terms

1. Calculate beta values This number should be 6. 4 2. Set up a column for the p. H value 3. Calculate [OH-] 4. Calculate D =10^(-(14 -A 3)) =1 + $J$5*B 3+$K$5*(B 3^2)+$L$5*(B 3^3)+$M$5*(B 3^4) 5. Calculate alpha 0 6. Calculate alpha 1 7. Calculate alpha 2 =1/C 3 =$J$5*B 3*D 3 =$K$5*B 3^2*D 3 8. Calculate alpha 3 and 4 in a similar fashion

Note that at p. H < 6 all of the lead is present as Pb 2+ This graph indicates that if our instrument is measuring Pb 2+ then we Prepare the sample we need to have a p. H of less than 6

GIGO Measurement of Lead Depends on: Chemistry of Lead for Separations Chemistry of Lead for Creating a signal Chemistry of Lead for Creating Background Chemistry of Lead for the Stability of the Signal Garbage In = Garbage Out

Measurements based on Pb. S

Measurements based on Pb. S 1820 Frederick Acum London

“ 1 part of acetate of lead May be detected by means of it in 20000 Parts of water. ”

1820 Sulphuretted water cupellation LOD ppm ppb ppt 8000 B. C. E. 1000 C. E. 1900 1990 2000

More Pb. S measurements -log Ksp Ag 2 S=49

Internal solution fixed in Ag+ Suppose we are using a lead ion selective electrode to measure Pb 2+, can We use any p. H less than 6? Soln Pb -log Ksp Pb. S=29 Pb 2+ S 2 Ag+ Pb 2+ S 2 S 2 controls 2 S S 2 S 2 - Pb 2+ Charge separation after motion of Ag+ leads to a potential across the Membrane = signal Pb 2+ S 2 - Ag+ Which controls -log Ksp Ag 2 S=49 Which controls Ag+

GIGO Measurement of Lead Depends on: Chemistry of Lead for Separations Chemistry of Lead for Creating a signal Chemistry of Lead for Creating Background Chemistry of Lead for the Stability of the Signal Garbage In = Garbage Out

Other Alpha Plots are also useful If we want to separate lead on an anion exchange column form the Pb. Cl 3 - species. Which line would that be? And what conc. Cl would we want?

GIGO Measurement of Lead Depends on: Chemistry of Lead for Separations Chemistry of Lead for Creating a signal Chemistry of Lead for Creating Background Chemistry of Lead for the Stability of the Signal Garbage In = Garbage Out

Lead Chloride, while useful for an anion exchange separation is a problem Because of it’s low vapor pressure Water is shown for comparison. What this means is if you get about 700 o. C You will have a large vapor pressure for Pb. Cl 2 which means you lose Stuff from solution

GIGO Measurement of Lead Depends on: Chemistry of Lead for Separations Chemistry of preparing the sample Chemistry of Lead for Creating a signal Chemistry of Lead for Creating Background Chemistry of Lead for the Stability of the Signal Garbage In = Garbage Out only instrument you have is a…. . UV-Vis Spectrophotometer UV-Vis monitors valence shell electrons Need to convert Pb to something that a. Has UV-Vis activity b. That can be selective toward Pb binding c. That can be separated from other binding metals

Not water soluble Loss of a proton makes this a good Complexing agent if mixed with Aqueous Pb 2+ What problems can we run into? 1. p. H not high enough to remove proton 2. p. H too high and results in lead hydroxide formation

Need to consider this a separation D Higher p. H To get reproducible results you will need to Set a standard procedure for number of Shakes and total time.

Also not water soluble Non-Water soluble

Other Considerations? False Positives Any other metals (including Mg 2+!!!) can cause a color change The chalk used to line the interior of your Protective gloves can cause false positives Solution? Selectively complex other metals and leave behind the lead!!!!

Which complexing agent would you use? Want low value for lead High value for others CN might be good BUT!!!!!

Iron ferricyanide Serves as an Oxidizing/reducting reagent Add CN to get rid Of Cd, Hg, Ni, Ag, and Zn, But Also add Citrate to pull The iron from ferricyanide To citrate form.

Mild oxidation of the unreacted Dithizone results in a dimer linked by a S-S bond which absorbs at 420 (see spectra 2). More extended oxidation results in cyclization with a product that absorbs at ~610 to 620 nm. Estimated molar absorptivity of the dimer is 30000 to 49000

Some “Data Considerations” How will you choose a wavelength from which to make a calibration curve? How will you determine if you still have unreacted dithizone contributing to Your signal? How will you quantitate the absorbance at the wavelength you choose?

How will you choose a wavelength from which to make a calibration curve? 1. Want a region where the signal does not change rapidly (the top of a peak) 2. Want a region where the analyte signal has the least contribution from the background (peak of Pb-complex) How will you determine if you still have unreacted dithizone contributing to Your signal? 1. Monitor wavelength of peak in the 600 region or deconvolute the data How will you quantitate the absorbance at the wavelength you choose?

Method 1 Monitor B at wavelength where only B absorbs and at the wavelength of interest Make a calibration curve at those wavelengths with standards for The background (unreacted dithizone); determine molar absorptivities Calculate concentration of unreacted dithizone for the measurement of Pb by Use of the calibration curve for unreacted dithizone Calculate the absorbance due to unreacted dithizone

Measurement Background A Method 2 Much easier And makes no Assumptions about What is contributing To the background Set a baseline across the bottom of the peak The difference in absorbance between the two is the background corrected signal Baseline estimation Use this lab to introduce another data manipulation

Use this lab to introduce another data manipulation Method 3 – assess contribution by assuming Gaussians

Assume absorbance peak is Gaussian in the energy spread photons e Energy of The absorption bands Energy levels are randomly populated By Temperature Frequency = absorption Std~(first guess) width at ½ peak ht Energy of light absorbed

Deconvolution 1. Get the absorption spectra

Deconvolution 1. Assume absorbance peak is Gaussian in the energy spread 2. Convert data from A vs wavelength to A vs energy Notice the 2 curves look Different!

Deconvolution 3. Using your data estimate: center of peak (mean) standard deviation amplitude A std mean

Wavelength, nm Frequency, Cm-1

Sum of all the bands Conversion to energy =10000/A 10 Guess four absorbance bands Value to be minimzed =(H 10 -B 10)^2 Calculated bands based on a Gaussian eq

energy wavelength Minimize Target cell Prevent solver from giving You non-plausible (negative) numbers

Plot the wavelength based absorption data And superimpose the data generated by solver

Now sum all the individual bands and see if you get a low sum of sq differences Some deviation here But generally pretty darn good

At the wavelength you are interested in Go to the column of data representing that Single absorbance band here I use 550 and find the max =max(data range) This will be your absorbance of the band Without the contribution from the other bands Our “signal” Go to 550 and use the A from this band Only!!! (all other absorbances represent Background contributions)

Chemistry titrimetric ppm LOD cuppellation ppb Suphuretted water dithizone ppt 8000 B. C. E. 1000 C. E. 1900 1990 2000 This method resulted in the first public health Awareness of lead as an issue for children Baltimore, Department of Public Health

GIGO Measurement of Lead Depends on: Chemistry of Lead for Separations Chemistry of Lead for Creating a signal Chemistry of Lead for Creating Background Chemistry of Lead for the Stability of the Signal Garbage In = Garbage Out Convert lead to some compound which can Be measured by some instrument (what ever happens to Be available in your lab) Suppose you only have a fluorimeter!

Calcein Blue Chromophore – part of molecule sensitive to light “Selectivity” arm – complexes the metal ion and turns On and off fluorescence

Excited State Proton transfer 480 -490 nm emission 18 -33 ns duration 320 nm excitation p. H 6 -8 Carboxyl groups only deprotonated Note role of resonance here Absorbance spectra Emission Spectra, excitation at 320

Excited State Electron transfer 350 -360 440 -460 H-N p. H 8 -11 Ground state phenolic deprotonation

Key point so far – Excitation is p. H dependent Therefore the emission location and intensity is also p. H dependent If the solution is fluctuating in p. H will not get a linear working curve. Since you have to control p. H for the chemical signal, need to also consider The role of p. H in the form of the lead that is present.

Why might Pb quench the emission? Lead quenches emission

Structures as determined from NMR

GIGO Measurement of Lead Depends on: Chemistry of Lead for Separations Chemistry of Lead for Creating a signal Chemistry of Lead for Creating Background Chemistry of Lead for the Stability of the Signal Garbage In = Garbage Out Convert lead to some compound which can Be measured by some instrument (what ever happens to Be available in your lab) Suppose you only have an IR!

Need to convert Pb to some form that is amenable to IR and/or Raman spectroscopies. 1. React lead with some reagent This data can Be found in The appendix To “Sublime Lead” web page

Need to convert Pb to some form that is amenable to IR and/or Raman spectroscopies. photon Change in bond length Pb 2+

Key Data Manipulation Concepts from the Lab IR instrument allows you to set the number of waveforms that you Will average. You will need to enhance the sensitivity near the base of one peak so That you can see the background fluctuations in a single scan Repeat for 4 scans Repeat for 9 summed scans Repeat for 16 summed scans, etc. What do you think you will be asked to observe?

A Case of Forensic Chemistry: Art and Forgeries Lead Tin II, Paolo Veronese, Allegory of Love Lead Antimonate Peter Rubens, The Dying Seneca Lead Tin I

Forensic Art Chemistry

Two Sb octahedra Linked via vertices to a) eight pointed polyhedra Of Pb & b) Hexagonal bipyramid Lead Antimonate Lead Tin II Chains of Sn octahedra Joined by Pyramidally Coordinated Pb(II)