Chemistry 223

Designing an Analytical Method

Fall, 2009

BRING YOUR COPY OF HARRIS TO THE LAB.

All semester, indeed in most labs you've ever done, you have been told how to do experiments ("Heat to
60°C," "Weigh 0.2 g."). The practice of quantitative analysis requires the analyst to DEVELOP methods
as well as to APPLY them. To give you a flavor of how to develop a method, this lab will guide you to
write a procedure for the analysis of a nickel ore sample. You will turn in a lab report after one week,
explaining how you will solve the problem of analyzing the ore sample. You will also carry out the
procedure you devise; you will then write a report after two more weeks on the nickel determination you
have carried out. If you devise a good method, your results will work well. Make bad choices, and the
precision will be poor. YOU make the decisions, YOU reap the rewards! The TAs will grade your first
(method design) lab report for clarity, logic, and accuracy. You will find for yourself when you're part way
through following your own instructions whether you did an adequate job.

While there will be a post-lab quiz for Week One (developing your procedure), there will NOT be post-lab
quizzes the remaining weeks of the semester. Since no two groups will use identical procedures,
devising a fair quiz is difficult. Furthermore, the reason we gave post-lab quizzes was so you wouldn't
quit thinking about the lab after you did it. On this lab, your ingenuity and focus will so heavily inform the
results that additional paperwork seems superfluous. Similarly, while there's a prelab quiz for Week One
and for Week Two, there is no pre-lab quiz for the last week of the lab. The course "curve" (the
guarantees for minimum number of points to achieve a particular letter grade) reflect this.

The parts of the lab are:

I. List the Universe of Possible Methods

II. Estimate the Amount of Analyte
III. Catalog Expected Interferences
IV. Narrow the Possible Techniques to Those Consistent with Expected Amounts and Interferences
V. Write Out a First Estimate of How to Carry Out Each Technique (Including Equilibrium or Kinetics of
Reactions as Appropriate). Decide on Sample Pretreatment
VI. Compute Masses, Volumes, and Other Signals Expected
VII. Estimate Errors
VIII. Discard Methods with Inadequate Detection Limit, Dynamic Range, or Precision
IX. Among Remaining Methods, Choose Based on Any Additional Available Criteria

In weeks 2 and 3, you'll make use of the results of the above body of work to analyze an unknown.

Students will work in groups. The 3 people on one side of a lab bench will form a single team. If there
are only 2 people on a bench, they can work as a pair or absorb a single person from another bench. If
there is only 1 person on a bench, they should preferably join a pair of people in need of a third. If (and
only if!) the number of students in a lab section is 3N+1, N an integer (so that there's no way for everyone
to be in 3's and there are no spontaneous groups of 2), one of the 3-somes should split so that the final
grouping of 3+1 becomes 2+2. In contrast to all the other labs this semester, each group will turn in a
single report and get a single grade. You will find that splitting up the work so that each group member
spearheads computations on one method will be the most effective way to proceed.

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 The sample you will plan to analyze is a mineral object, thought to be a siderite meteorite.
Such meteorites are composed mostly of iron and magnesium but also contain 1-10%
nickel. The metals are present as carbonates, phosphides, and sulfides.

I. List the Universe of Possible Methods

Methods we have NOT used previously, and that are NOT available to you (but are commonly used in
well-instrumented labs) are:
a) Inductively-coupled Plasma Mass Spectrometry
b) Inductively-coupled Plasma Emission Spectrometry
c) Flame or Furnace Atomic Absorption Spectrometry
d) X-ray Fluorescence
We list these so that, if you're ever faced with this sort of analysis in the Real World, you'll consider them.

Methods that we have used previously or that are discussed sufficiently in Harris to be worthy of your
consideration include:
A. EDTA Titration (forward or reverse – whichever works better)
B. Quinoxoline Complexation with Spectrophotometric Determination (using pre-separation to
remove interferences)
C. Quinoxoline Complexation with Spectrophotometric Determination (using multiple absorbance
measurements at multiple wavelengths and standards for any interfering species to determine the
amounts of both nickel and interferents)
D. Dimethylglyoxime Precipitation and Determination by Gravimetry

II. Estimate the Amount of Analyte

Suppose the meteorite weighs 15 g. You don't want to destroy the whole meteorite in doing the analysis.
You can chip ~ 1 g from the meteorite and grind it up.

FOR A 5 g SAMPLE: compute the range of Ni masses expected and the range in the number of moles
expected.

Minimum expected mass in sample _______ g Maximum expected mass in sample _______ g.

Minimum expected moles ____________. Maximum expected moles ____________.

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III. Catalog Expected Interferences

The interferences are Fe, Mg, metal oxides and hydroxides, and possibly CO3=, P3-, or S=. For each:
- List possible redox states that must be considered.
- Are the species soluble in acid? In base? What nickel salts are highly soluble? Are Fe and Mg
salts of the same anions soluble?
- Look up the solubility product of FeS, MgS, NiS, FeCO3, Fe3P2, Ni3P2, Mg3P2.
- Why can we ignore most Fe(II) compounds?

Compound Ksp If Ksp not found, why not?

FeS
MgS
NiS
Ni3P2
Fe3P2
Mg3P2
FeCO3
Fe2(CO3)3
Fe2O3
NiO
MgO
Mg(OH)2
Ni(OH)2
FeOOH
Other Fe(III) oxy-
hydroxides

Look up the pKa's of the relevant acids: H2S, H2CO3, PH3. Note that both hydrogen sulfide and phosphine
are HIGHLY toxic.

From what you have determined so far: RECOMMEND whether to dissolve the specimen in acid, base, or
neutral water AND explain why. We'll figure out which acid or which base (if one of those is what you
choose) later. Also, recommend whether we should try to maintain the oxidation state of all the elements,
or if we should try to oxidize some or reduce some.

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IV. Narrow the Possible Techniques to Those Consistent with Expected Amounts and Interferences

Clearly, the 5 g of sample is going to have to be diluted into a reasonable volume of solvent or buffer. We
don't yet know what that volume will be. Thus, let's compute what amounts and concentrations will be
present for various amounts of dilution. For amounts in aliquots, assume the amount of analyte is mid-
way between minimum and maximum expected amounts.

Volume of diluted Molarity for Molarity for Approximate Approximate

Sample Minimum [Ni2+] Maximum [Ni2+] moles in 5 mL moles in 25 mL
aliquot aliquot
100 mL
250 mL
1000 mL

V. Write Out a First Estimate of How to Carry Out Each Technique (Including Equilibrium or Kinetics of
Reactions as Appropriate). Decide on Sample Pretreatment.

This is where each member of the group should take the lead in looking at one of the methods. Assign
one member to look at EDTA titration, one at DMG gravimetry, and one at quinoxoline complexation.

For each of the techniques in I.A. – I.D., once Ni2+ is in solution, write out:
- the reactions that Ni2+ undergoes.
- any redox reactions needed to remove interferents
- any pKa's for reactants that haven't yet been tabulated
- the equilibrium constants for all reactions
- the range of pH in which one wishes to work and what happens if the determination is attempted
outside that range.
- what buffer would be best to use when carrying out the method
- what effect that buffer would have on the other components

Now that you have all the chemistry listed, suggest a procedure for sample preparation. Your explanation
will start out with grinding the sample. Should you dry the sample? If so, at what temperature? If it's too
low, you won't succeed in drying it, and if too high, you might oxidize some of the sulfides or phosphides,
leading to an erroneously high measured [Ni2+]. Next, specify how much sample to weigh (yes, I know it's
~ 5g. Specify an acceptable range. Is it 5.0000±0.0001 g? 4.8 to 5.2 g, measured to 2 places? To 4
places?). Specify how to dissolve the specimen. What acid, base, buffer, or other solvent should you
use? What volume? What temperature? After the dissolution step, what additional materials need to be
added, in what quantity, to carry out what steps? Hint: how will you get rid of the sulfide so you don't form
pyrite (fool's gold, FeS) as a precipitate in basic solution? Should the operations be carried out on the
bench top or under the hood? See how the steps that you've been told to follow all semester are
determined in light of the chemistry and safety?

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VI. Compute Masses, Volumes, and Other Signals Expected

Now for the fun! For each of the techniques in I.A. – I.D., what behavior would we expect? Choose the
volume into which to dilute the specimen you dissolved in step V. Specify whether to dilute with water or
with buffer (and, if buffer, what buffer?). Use the table in step IV to help you out.

FOR TITRATION METHODS: give an approximate value for the optimum concentration of the titrant. For
a 25 mL aliquot, compute the volume of titrant required to reach the equivalence point. Compute the
titration error (overshoot or undershoot when the indicator will recognize that you've hit the endpoint).
Simulate the titration curve; will there be a sharp enough inflection to see an endpoint?

FOR SPECTROPHOTOMETRIC METHODS: give an approximate value for the absorbance of a 5 mL

aliquot processed with the appropriate complexing agent. What concentration of complexing agent
should be used? Is the complexing agent soluble in the buffer of choice at the necessary concentration?
If the absorbance is too high, by what additional factor should the sample be diluted? If the absorbance is
too low, would you be better off with an initial dissolution volume, and is that volume practical?

FOR GRAVIMETRIC METHODS: specify the approximate concentration of the precipitating agent (Harris
explains this, P. 631-635). Specify the volume of aliquot to take and the volume of precipitating agent to
add. Estimate the mass of precipitate and the solubility error i.e. the fraction of the analyte still in solution
because Ksp isn't 0.

VII. Estimate Errors

Do a propagation of error calculation for each method. You will have a deterministic error for the
gravimetric and titrimetric methods because of indicator/endpoint error. Background will cause error in
the spectrophotometric method IF the complexing agent reacts with any of the interfering species AND
you haven't separated the interferents. If the interferents are present, you'll have to run working curves
for the interferents so you can compensate for their presence. All methods will have random errors.
From your experience this semester, estimate the magnitudes of expected errors. Each member of your
group will do a propagation of error computation for the method on which they are taking the lead.

VIII. Discard Methods with Inadequate Detection Limit, Dynamic Range, or Precision

Now compare the methods. Are there any where the signal is so low or the error so high (over 1%) that
the method can't be used? Are there any where the signal is so high that a greater dilution should be
used? Explain your reasoning.

IX. Among Remaining Methods, Choose Based on Any Additional Available Criteria

If you find there are no methods that will work, so state (Hint: at least one will work.).

If you find there is only one method that will work, so state.

If you find there is more than one method that will work, choose which one YOU would use and justify
your choice.

Your combined report MUST list the names of those who are collaborating.

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"Nickel is green in solution. Why not measure the absorbance directly?" The molar absorptivity of
Ni(H2O)62+ at 388 nm is 5.3 L mol-1 cm-1. [Wannowius, K. J.; Krimm, K.; Elias, H., "Visible spectra of the
nickel ethylenediamine complex species Ni(en)32+, Ni(en)2(H2O)22+ and Ni(en)(H2O)42+ from kinetic
studies," Inorganica Chimica Acta, 127(2), L43-L44 (1987).] Since the minimum absorbance one can see
is about 0.001, how does the detection limit compare to the numbers you found in Section IV? Can one
quantitate at this low level (think error propagation)? What concentration would be needed to allow
spectrophotometric precision of 1%? Is this obtainable from the meteorite sample?