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Transcript of 1 CHEM 511 ADVANCED QUANTITATIVE ANALYSIS R. S. Houk, B27 Spedding, 4-9462, [email protected]...
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CHEM 511 ADVANCED QUANTITATIVE ANALYSIS
R. S. Houk, B27 Spedding, 4-9462, [email protected]
Office: 8:30 – 10 AM T Th, other hours as available
Grading: system will be usedHour exam I 25%Hour exam II 25%Final exam 30% (50% comprehensive, 50% material since last exam)Paper 20%
QUESTIONS WELCOME ANYTIME!
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NO FORMAL TEXTHARRIS, QUANT CHEMICAL ANALYSIS, 7th ED.SUGGESTED
www.chem.iastate.edu/courses.html
ACCESS TO EXCEL?
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CLASS OUTLINE
I. Overall Analytical Process
II. Sampling and Sample Preparation
III. Advanced Chemical Equilibrium
IV. Evaluation of Analytical Data, Accuracy & Precision
V. Miscellaneous Measurement MethodsImmunoassay Searching Spectral DatabasesElectrochemistry Elemental SpeciationKinetic Methods Activation AnalysisIn Situ Methods, Sensors Flow Injection AnalysisMeas. Binding Constants
VI. Scientific Writing
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PART I. OVERALL ANALYTICAL PROCESS
DEFINEPROBLEM
SELECTMETHOD
SAMPLINGSAMPLE
PREP.
MEAS.ANALYTES
EVALUATEDATA
Analyst Client
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METHOD INCLUDES ALL STEPS, NOT JUST MEASUREMENT
SOMETIMES PREPARE SAMPLE & MEAS. ANALYTES AT SAME TIME
RESULTS SOMETIMES INDICATE DEFICIENCY,TAKE & PREPARE NEW SAMPLES, EVEN RE-DEFINE PROBLEM
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DEFINE PROBLEM?
What is overall scientific question? Time constraints?- on-line meas.?
What type of anal. results needed?-qual or quant? Cost acceptable?-elements, compounds, or isotopes? -instrumentation
-personnel (usually cost more
*Nothing costs more than poor result! than insts.!)-sampling & prep.
Analysis done previously? Consult literature.General journalsSpecialty journalsReviews & monographsCompilations of official or approved methods (AOAC, EPA, …)Internet - websites, newsgroups, list servers - reviewed?
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TERMINOLOGY
ACCURACY - agreement between meas. value and actual conc.
PRECISION - reproducibility of repeated measurement
SYSTEMATIC ERROR, DETERMINATE ERROR, BIAS - all results off by consistent amount.
RANDOM ERROR, INDETERMINATE ERROR - some results too high, others too low, ~ evenly distributed.
MEAN & STANDARD DEVIATION (s) -absolute std. dev. - rel. std. dev. = s /
( )x
( )x
Confidence limits = x ts
n *Specify
n!
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CALIBRATION CURVE
SENSITIVITY = slope of cal. curve.
DETECTION LIMIT = analyte conc. or mass necessary to produce net signal = 3x (std. dev. of blank).Minimum amount of analyte that can be measured
*SENSITIVITY DETECTION LIMIT!!
SELECTIVITY - pick out analyte signal in mixture.
ONLY SAMPLES ARE ANALYZEDELEMENTS OR COMPOUNDS ARE IDENTIFIED OR DETERMINED.
SAMPLINGOBJECTIVE - to collect sample whose composition represents that of overall material to be analyzed, within acceptable limits.
Usually can’t analyze entire material, collect portion for analysis representative of whole material.
SAMPLE PREPARATIONOBJ - to convert sample into form suitable for analysis.
Usually dictated by instrument used & information required.-dissolution for elemental analysis, destroys chemical info.-organic comps. in soils extracted, then meas. by GC-MS …
Sampling & sample prep. prone to errors - loss or contamination.Best possible inst. produces wrong result if sample contaminatedor if comp. of sample analyzed that of original material!
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MEASURE ANALYTESOBJ - Select best method, optimize performance.
Usually done with instrument, even titrations.
Discuss special methods, don’t fit other courses.
EVALUATE DATAOBJ - to determine if data produced are adequate to solve original scientific problem.
Identified important analytes & potential interferences?
Detection limits?
Adequate accuracy & precision?
Do meas. results agree with “true” values? Reject outliers?
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EXAMPLE PROBLEM
Source of smuggled gold? Purely from one mine or melted & mixed? Use trace element composition to trace source of gold?
Cost of instrument insignificant relative to problem.
Gold very valuable, analyze sample directly, no dissolution, small samples.
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“Gold can be melted and recast and is therefore virtually untraceable”
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Select MethodObjective : ID elemental impurities in gold metal.
“Suspected theft!”
- Analyze solid directly, hard to dissolve. Don’t want to destroy entire sample to determine if stolen!
- Multielement measurement, ID as many elements as possible.
- May not need to quantify elements, in most cases, depends on differences in trace elements in nature.
- Need fast results. Can’t hold suspects in jail forever unless have evidence to charge them.
-Data adequate to stand up in court
Method of choice:
1. Use laser ablation to sample gold
2. Then ICP-MS to ID trace elements
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REs Much lowerREs!
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SAMPLER SKIMMER
IONLENS
ION SAMPLING INTERFACE
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SamplingOne spot may be contaminated or lacking importantelement.
Raster laser around surface of sample. Dig various pits.
When melt gold & recast, reasonably homogeneous. Probably OK just to shoot at upper layers with laser.Gold also resistant to oxidation, so upper layers
representative of whole sample.
Sample PreparationLaser ablates solid gold into small particulates, carried by
Ar stream, then atomized and ionized in ICP.In this case, actual instrument does the sample
preparation!!!
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Measure AnalytesShoot for 5-10 minutes, 10 Hz, 600 - 1200 shotsScan whole spectrum. Might be unexpected elements!ID elements from m/z values & isotope ratioAveraged results OK, ID trace element pattern of whole sample.
Evaluate DataAre trace element patterns actually different from different gold sources?Simple pattern adequate? Apply pattern recognition.If gold is mixture, pattern is linear combination of patterns of
individual gold source. Check method - analyze gold SRMs.
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Watling, Spectrochim. Acta Part B 1994, 49, 205-219.
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*Problem publishing results because didn’t quantify, didn’t use internal standard, etc.
Not necessary!! Would have been waste of time!
*Don’t produce more information than needed!
Make Decision Suspect guilty or innocent? Evidence adequate
to go to court?
Return gold to proper owner.
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Sampling & Sample Preparation
Refs: Skoog, West, Holler, Anal. Chem. SWH, 7th ed., Chap. 32, 8th ed., Chaps. 34-36.Kratochvil & Taylor, Anal. Chem. 1981, 53, 924A. (AC)
C. A. Bicking, Treatise on Anal. Chem. 2nd ed., Vol.1, Part 1, Chap. 6, pp. 299-359
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Objective: Collect sample that represents actual composition of overall material, within acceptable tolerance
representative sample
*Note: still important consideration for on-line process analysis, ie., sensors, probes, etc, that analyze sample as is w/o preparation.
Several questions: does small probe or sensor address enough sample for results to be rep. of whole?
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Main Issues:
1. Sampling error significant relative to overall error?
2. Consider particle size at which heterogeneity begins. Sample enough particles to get rep. sample? Done within context of whole method.
3. Minimize contamination & loss. More later, also related to sample prep’n
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Harris p 7
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Sampling error random std dev = sS
Analytical error random, std dev = sa
Both errors random, variances add
sD = overall std dev in means
sD2 = sa
2 + sS2
1. Useless to use very precise analytical method (small sa) with sloppy sampling (large ss)
2. If material can’t be sampled with small ss, might as well use cheaper/faster anal. method, so long as sa < ss !
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Collect Gross Sample, reduce size to analytical sample
Dictated largely by sample matrix
Matrix Size at which heterogeneity begins
Homogeneous gas or liq. Atomic / molecular
Suspended particles Size of particulate
in homo gas or liq. (colloids < 1 µm
smoke 0.1-10 µm)
Heterogeneous gas or liq. Macro scale, may need spatial
(e.g. upstream & downsteam characterization
of spill)
Gross Sample >
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Size of gross Pure metal atomic / molecular
sample Heterogeneous metal particulate / grain sizes
such as fine grainsC
Coal (v. heterogeneous) many diff. sizes & types of
particulate
analyze just one chunk v. misleading results!
Waste of time & effort unless get rep. sample
SAMPLING SOLIDS
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How much gross sample?
WR2 = Ks
W = sample mass R = RSD (%) in sample composition
Ks = sampling constant = sample mass required to limit sampling uncertainty to 1% (with 68% confidence)
Meas. Ks exp.
Signal
mass Na
ntss
170
210
250
290
0.1 1 102 5
Conf.
interval
Ks = 30 g
Same mean in each case
Sample mass, g
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Sampling
* Sample analyzed must represent overall composition of whole material, within acceptable limits.
Steps:
1. Collect gross sample - section of overall material that is large enough for composition to be representative of whole material.
2. Reduce size of gross sample to lab samplee.g., 1 kg gross sample 1 g lab sampleReduce particle size. Loss? Contamination?
3. Prepare lab sample for analysis (often dissolve)
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Size of gross sample?
Gas, liquid, solution:
-Rel. homogeneous, small sections will likely represent composition of whole.
-Easy to collect sample, only small sample required
Solid:
-Heterogeneous, individual particles prob. differ, must collect enough particles for rep. sample, so gross sample may be very large
e. g. coal
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SAMPLING STATISTICSHARRIS p 646
Mixture of particles, nA of type A & nB of type B
p = probability of drawing type A = nA/(nA + nB)
q = prob of drawing type B = nB/(nA + nB) = 1 – p
Withdraw N particles at randomSampling error = std dev = ss
Npq ss
Ex p 6461% KCl particles + 99% KNO3 particlesCollect 104 particles.How many are KCl? What is std dev of many such collections?
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Npq ss ss ~ N1/2 Rel error = ss/N ~ 1/N1/2
1. To reduce ss/N appreciably, must greatly increase N!
2. N = # of particles If particles are large, sample mass also large!
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Ex. Solid mixture of 2 types of particles (composition P1 + P2)
density d1 + d2, p = fraction of total in one form
How many of these particles (n) must be collected so that comp. of gross sample = that of total material within std dev. = sr (RSD)?
= # of particles in avg. avg.
gross sample density composition
2212
21 ))()(1(Ps
PP
d
ddppn
r
(Ch. 8 SWHC8)
Smaller sr (high accuracy)
large ( p1 - p2) (more heterogeneity)
Large n
large gross sample
Important to define problems --- what level of accuracy required? No use using larger gross sample than necessary.
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If n large, sample large solid particles, gross sample might be v. large indeed
- railroad car full for coal.
- cone & quarter many times.
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Sampling Procedures
1. Homogeneous liquids - just lower bottle cap, pull out. Or pump out through line,
esp. process stream.
2. Liquids & particulates (river waters, eg)
a) liquid only, filter out particulate
- size of pores thru filter? - may change equilibrium in supernatant
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Pb2+ sorbs readily, much of Pb in water may actually be sorbed to particles! If remove colloids, meas. [Pb] in H2O too low!
Problem? Depends on results required
Colloidal particle in H2O
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3. Gases -
a) expandable bag or balloonb) pass through filter or solvent, strip out analyte
4. Compact solids - auger or corer crush whole solid
5. Particulate solids
a) thief - slotted bottle inserted into collection of particulates
comes out with rep. material.
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Reduce size of gross sample
Instrument can't analyze massive amount of matrix.
Subdivide gross sample into smaller lots,each lot still represents overall gross sample
Often involves reducing particle size at which heterogeneity begins.e.g. grind solids
41
Examples
1. Sea water (elements very low concentration)a) evaporate 1L to 5 mL, increase analyte conc. 1000/5 = 200Xb) also matrix (Na, K, Ca, Cl)
Pour 1L through chelating column, reduce size of gross sample, preconcentrate analyte,remove tough matrix, all at same time!
Then elute in ~ 2 mL.
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2. Coning and quartering coal, truckload few g! * Analyte stable during sampling? - acidify water Do additives - coagulation of blood contaminate sample? (prevent w. EDTA) sample?
Contamination Control in Trace Element AnalysisM. Zief & J. W. MitchellChemical Analysis Vol 47, Wiley
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Sample Preparation
Objective - convert lab sample to form that can be analyzed by appropriate methods with acceptable accuracy and precision.
Refs. Jarvis chap.R. Bock, Handbook of Decomposition MethodsBlackie, London, 1979.www.sampleprep.duq.edu/sampleprep/
* No single best sample preparation procedureChoice decided by requirement of overall problem.
45
Why analyze sample as solution?
1. Many techniques require solution2. Solution homogeneous, simplify presentation of representative sample to instrument3. Relatively simple to prepare standards with solutions - just add aliquots of analyte elements
a) some elements incompatible (Ag+ & Cl-)b) for many elements accumulative error of pipetting adds up fast, also contamination
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4. Easy to produce blank (sample that lacks analyte), measure blank right before/after sample, evaluate correction for interference or contamination5. Procedures for producing and storing solutions well established, not perfect but problems readily anticipated.
Disadvantages of dissolving samples:
1. Time consuming and difficult, especially ceramics, refractory or noble metals
2. Can introduce additional matrix elems. & impurities
3. Destroy spatial information
47
Suppose sample is already in solution, preserve until analysise.g Canadian Geo. Survey. Transport water back to instrument for analysis.
1. Stability during storage ?
Fe+3 + 3 OH- ‡Fe(OH)3 x H2O KSP
H2O ‡ H++OH- KW
If Fe(OH)3 x H2O forms, many other trace metals will coprecipitate, must acidify sample.
48
* Solution for elemental analysis usually acidic during storage, and measurements usually done on acidified soln. If must make neutral or basic, sometimes OK during separation / preconcentration steps. HNO3 usually preferred
2. Leaching from or loss to container also problem:
Elemental analysis - plastic only, Teflon, no glassware!Preclean with acid & leach.
*How evaluate contamination? Measure blank! Standard additions!
49
2. Correct oxidation states, other chemical forms?
e.g. Se(0) Se(IV) Se(VI) [Se(-2)]
SeO3-2 SeO4
-2 Se in proteins
Se(IV) SeH4 (g) quant.
Se(VI) SeH4 poor yield, erratic
Se(0) no SeH4
Se-proteins
Therefore, to measure total Se,
must be sure all Se present as Se(IV) first!
NaBH4 For hydridegenerationAAS
50
3. Concs. high enough? If not:
a) Evaporative preconcentration.
* Avoid heat to dryness, severe loss of volatiles.
b) Preconcentration and matrix removal.
Some form of LC.
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Original sample is solid. Must dissolve.** Why dissolve sample at all? Dry first? Or analyze “as received?”
I. Dry ashing (esp. for organic samples)
- heat at high temp (maybe 600 oC), maybe also O2. - burn off org. matrix. - dissolve residue in acid. - seldom used now - many elements lost (Ag, As, Au,
Be, Cd, Co, Cs, Cu, …… Hg, Pb, …Se, Sn, Tl)!
*Always hard to reproduce partial losses. Bad idea to try to correct for low recovery.
52
II. Wet Digestion in AcidA. Acids Used1) Variety of acids, dep. on how tough sample
is.2) Safety critical! Literature review or experience
essential, esp. with HClO4 & HF.
3) Refs. R. Bock, A Handbook of Decomposition Methods,
Blackie, 1979. Z. Sulcek + P. Povandra, Methods of Decomposition
in Inorganic Analysis, CRC Press, 1989.I. Jarvis, Sample Prep. for ICP-MS, in Handbook of ICP-MS, 1992.
53
SAMPLE DISSOLUTION
DIGEST SOLID?ICP-MS: HNO3 , H2O2 ONLY IF POSSIBLEHF, HCl, HClO4 IF NECESSARY
SAFETY!!APPROVED PROCEDURES
MAKE UP IN AQUEOUS HNO3
TYP. 0.1 to 1% SOLUTE IN 1% ACIDKEEP ACID CONC. CONSTANT
TMAH (Me4N+OH-) IN H2OBIO. MATERIALS
54
LOW BLANKS?
NALGENE OR POLYETHYLENE OK FOR DIW
TEFLON CONTAINERS PREFERREDFOR ACIDIC SAMPLES
ACID-WASH:10% HNO3 + 5% H2O2 + 5% HF (CAREFUL!!)WARM OVERNIGHT OR LONGERRINSE & STORE IN DIW
DUST-FREE ENVIRONMENTKEEP SAMPLE BOTTLES CAPPED
55
CLEAN ACIDS?SUB-BOILING DISTILLATION
56
Impurities in HNO3
ACS Reagent Commercial grade high-purity
Pb 0.02 0.2 0.3
Sn 0.01 0.1 1
Zn 0.04 4 8
Cr 0.05 6 130!
Cu 0.04 20 4
SB distilled
ng/g
57
Clean Room - minimize contamination from particulates in atmosphere.
J. Moody, AC, 1982, 54, 1358A-1376A.
Boutron, Fresenius J. Anal. Chem. 1990, 337, 482-491.
Blower
HEPA
Hood Benches
Restrict accessPositive air pressure to outside
METAL-FREE?
58
Class 10,000, 1000, 100, 10
# of particulates/unit vol.
Pb in air Fe Cu Pb Cd
St.Louis 19g/m3 Ordinary Lab. 0.2 0.02 0.4 0.002
Rural SE Mo. 0.77 Classroom 0.001 0.002 0.0002 nd
Lab. Air,NIST 0.4 Clean hood 0.0009 0.007 0.0003 .0002
* Purify acids and dissolve samples! Solution less likely to be
contaminated with dust than solid?
* Clean rooms based on semiconductor prep’n. based solely on
minimizing particulates, not metal free.
Trace Elements in ParticulatesConc, g/m3 air
59
CHECK CLEANLINESS USING CAL. CURVE
60
Mineral Acids for Dissolving Samples for Elemental AnalysisSee Jarvis, p. 174 Table 7.1HNO3
Conc. HNO3 = 68%, 16 M, boils at 122 oC Strong oxidizing agent if present > 2 M Yields highly soluble nitrates. Little explosion danger, unless stored near organics! (Fritz group)!!!Never!!! Never!!! Nein!! Nein!! Niemals!! Niemals!!HNO3 alone: metals, alloys, bio. materials. Prefer if can get away with HNO3 alone. Tougher samples use HNO3 mixed with stronger ox. agent (H2O2 or HClO4). - HNO3 goes to work 1st, dissolves bulk of matrix. - HClO4 or H2O2 then kicks in, dissolves more refractory
residue.* Never use HClO4 alone!! Nein!! Nein!! Niemals!! Niemals!!
62
HCl (12 M, 36%, bp 110oC)
Useful for many metals and oxides, esp. if form soluble chlorides (e.g. Al)Not oxidizing agent at all
Weak reducing agent, seldom used for organic materials.
Potential loss of elements with volatile chlorides (As, Sn, Pb, Hg, Se,…)
Sucks in ICP-MS, ClO+ & ArCl+
OK for most other atomic spectroscopy
63
HF (29 M, 48%, azeotrope 22 M, 38%, bp 112oC)
Effective for silicates
SiO2 (s) + 6HF (aq) H2SiF6 (aq) + 2H2O
H2SiF6 (aq) SiF4 (g) + 2HF (aq)
Boil off Si from rock matrix!
Always used with oxidizing acid (HNO3 or HNO3/H2O2) High ox. states. in final solution.
V. dangerous if spilled! Need full protective clothing, protection, face shields, special cleanup kits!
Not strong acid, Ka = 6.8 x 10-4
HClO4 (azeotrope 72.4%, bp 203 oC)
Everett + Graf, Handbook of Lab. Safety, N.V. Steere, Ed.,
CRC, Cleveland.
Schumacher, J.C., Ed. Perchlorates- Their Properties,
Manufacture & Uses, ACS Mono., No. 146, Reinhold, 1960.
* Never use HClO4 alone! Nein!! Nein!! Nein!! Niemals!!
Hot, conc. azeotrope v. powerful ox. agent, explosive reaction
w. org. matter and some metals.
Cold or dilute acid little hazard.
Use HClO4 in conjunction with HNO3 (4/1 HNO3/HClO4 or more!)
- HNO3 oxidizes & dissolves most material,
then distills off at ~ 122oC.
- cold HClO4 no ox. props. until 140 oC, so doesn’t attack sample
until HNO3 boils off.
- heat further, HClO4 brings remainder of sample into solution.
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Explosion hazards
C2H5 - OClO3 + other organic perchlorates
Some dry (anhydrous) metal perchloratesesp. Mg (ClO4)2
Esp. from alcohols, fats, lipids!
Solid crystal of KClO4 or NaClO4
Inner cavity w. HClO4 or Et-OClO3,superheated
M(ClO4)n good drying agent, never use to dry org. liquid.Don’t use organic solvent in HClO4 hood!Use small amounts at first, test procedures, avoid heating to dryness.
66
Periodic Table of the Elements
103Lr
(260)
102No
(259)
101Md
(258)
100Fm
(257)
99Es
(252)
98Cf
(251)
97Bk
(247)
96Cm
(247)
95Am
(243)
94Pu
(244)
93Np
(237)
92U
238
91Pa
231
90Th
232
71Lu
175
70Yb
173
69Tm169
68Er
167
67Ho
165
66Dy
162
65Tb
159
64Gd
157
63Eu
152
62Sm150
61Pm
(145)
60Nd
144
59Pr
141
58Ce
140
8A18
7A17
6A16
5A15
4A14
3A13
Lanthanides
Actinides
109Une
(266)
108Uno
(265)
107Uns
(262)
106Unh
(263)
105Ha
(262)
104Rf
(261)
89Ac
227
88Ra
226
87Fr
(223)
83Bi
209
82Pb
207
81Tl
204
80Hg
201
79Au
197
78Pt
195
77Ir
192
76Os
190
75Re
186
74W
184
73Ta
181
72Hf
178
57La
139
56Ba
137
55Cs
133
51Sb
122
50Sn
119
49In
115
48Cd
112
47Ag
108
46Pd
106
45Rh
103
44Ru
101
43Tc
(98)
42Mo
95.9
41Nb
92.9
40Zr
91.2
39Y
88.9
38Sr
87.6
37Rb
85.5
86Rn
(222)
85At
(210)
84Po
(209)
52Te
128
53I
127
54Xe
131
36Kr
83.8
35Br
79.9
34Se
79.0
33As
74.9
32Ge
72.6
31Ga
69.7
30Zn
65.4
29Cu
63.5
28Ni
58.7
27Co
58.9
26Fe
55.8
25Mn
54.9
24Cr
52.0
23V
50.9
22Ti
47.9
21Sc
45.0
20Ca
40.1
19K
39.1
18Ar
39.9
17Cl
35.4
16S
32.1
15P
31.0
14Si
28.1
13Al
27.0
2He
4.00
10Ne
20.2
9F
19.0
8O
16.0
7N
14.0
6C
12.0
5B
10.88B
2B12
1B111098
7B7
6B6
5B5
4B4
3B3
12Mg
24.3
11Na
23.0
4Be
9.01
3Li
6.94
2A2
1A1
1H
1.01 HF
HCl
ACIDS NEEDED TO KEEP ELEMENTS IN SOLUTION
67
B. Regardless of acid system, microwave digestion now best heating method by far*Microwave Enhanced Chemistry, Kingston & Haswell, ACS, 1997. http://www.sampleprep.duq.edu/sampleprep1) faster (compared to conventional heating)2) better control and variation of temperature3) can often get by with less powerful acids
*Many sediments go right into solution in HNO3 with proper microwave program, never fully dissolved whenheat with hot plate in HNO3 alone, unless use HF.4) easily, safely adapted to closed vessels, minimize lossof volatile elements, see Jarvis, p. 204.*Need oven specifically designed for digestion. Can’tjust slap samples in same oven used for cooking.Microwave energy directly excites rotations, esp. of H2O
68
MICROWAVE SAMPLE DISSOLUTION
SEALED VESSELSOK FOR VOLATILEELEMENTS
POWER REGULATED
SAFETY VALVES
69
70
. Can’t dissolve sample in acid? Try flux or fusion. Ref. Zehr and Zehr, Spectroscopy 6 (4), 44 (1992-3). REQD. Also Harris p. 652
Mixture of sample and inorganic salt(usually ~ 1/10 sample/salt)
Heat mixture until melts together. Thencool and dissolve in aqueous acid or water.
Crucible (Pt, Zr, Al2O3, carbon)heat
71
Li2CO3 732CNa2CO3 853 CK2CO3 903 C
Much hotter than acids!
m.p.
Particularly valuable for v. refractory materials, esp. ceramics and phosphors.Many fluxes Na2B4O7•10H2O
NaF/Na2B4O7 •10H2O Na2CO3/H3BO3
Na2CO3/Na2O2
*Different fluxes require different crucible. Some fluxes (Na2O2) eat up Pt!
72
When dissolve cake, salt element present•blank of flux, evaluate contamination•problem in some meas. methods, high level of salts in subsequent solution.
*1 g sample + 9 g salt, dissolve in 1000 ml 1% total solutes
only 0.1% sample!May lose volatile elements from high temp. melt
4222 MoONaMo ONa
These procedures prob. change chemical form of analyte elements, e.g., Cr2O7
2- & Cr3+
73
Related method specifically for Pt group elements(Ru, Rh, Pd, Ag, Os, Ir, Pt, Au)
Fire assay procedure*Very old --done by Egyptians for Au!Sample usually geo. matrix (suspected ore)Mix large sample (25 g) w. borax, Na2CO3, Ni, S8
Melt, physically separate NiS “button”. Pt group elements selectively dissolve in NiS buttonOther metals not.Then dissolve button soln. of Pt group elements (+ Ni).
74
FLUX INFO FROM CLAISSE
75
WWW.CLAISSE.COMWWW.CLAISSE.COM
Sample preparation by fusionfor AA and ICP analysis
Sample preparation by fusionfor AA and ICP analysis
76
What is a fusion?What is a fusion?
Oxide
Flux
Oxide
Flux
XRFXRF
AA
ICP
AA
ICP
1050 0C1050 0C
77
Examples of Fusion Solutions
Examples of Fusion Solutions
CopperCopper CeramicsCeramics
BauxiteBauxite CatalystCatalyst
78
Fusion ApplicationsFusion Applications
Cements, ceramics and glassmakers• Refractories, silica, alkaline oxides, alumina, iron oxides,
magnesia, titania, zirconia...
Mining• Sulfides, fluorides, silicates, rocks, soils, ores…
Metal producers • Slags, ferroalloys, alloys and steel• Aluminum, copper, silicon, zinc...
Others• University, environmental Labs, polymers, catalysts
Cements, ceramics and glassmakers• Refractories, silica, alkaline oxides, alumina, iron oxides,
magnesia, titania, zirconia...
Mining• Sulfides, fluorides, silicates, rocks, soils, ores…
Metal producers • Slags, ferroalloys, alloys and steel• Aluminum, copper, silicon, zinc...
Others• University, environmental Labs, polymers, catalysts
79
Flux: Lithium metaborate
Time: 10 min
Flux: Lithium metaborate
Time: 10 min
Advantages over microwave digestion
Advantages over microwave digestion
Acids :H3PO4 and H2SO4
Time: 50 min
Acids :H3PO4 and H2SO4
Time: 50 min
Al2O3:Al2O3:
FusionFusionMicrowaveMicrowave
4 to 5x 4 to 5x fasterfaster4 to 5x 4 to 5x fasterfaster
Acids : HF and HNO3
Time: 40 min
Acids : HF and HNO3
Time: 40 min
W2O5:W2O5:
80
Step 1Acids: H3PO4 and H2SO4
Time: 60 min
Step 2Acids: HNO3 and HFTime: 35 min
Step 3Acid: H3BO3
Time: 30 min
Step 1Acids: H3PO4 and H2SO4
Time: 60 min
Step 2Acids: HNO3 and HFTime: 35 min
Step 3Acid: H3BO3
Time: 30 min
Advantages over microwave digestion
Advantages over microwave digestion
(Chromite ore)(Chromite ore)
Time: 2hrs 5 min
5 different acids
Time: 2hrs 5 min
5 different acids
Flux: Lithium metaborate
Time: 10 min
Flux: Lithium metaborate
Time: 10 min
FusionFusionMicrowaveMicrowave
12x Faster12x Faster12x Faster12x Faster
HNO3
Hot plate acid digestionHot plate acid digestion
•Low or partial dissolution (SiO2, TiO2…)•Low or partial dissolution (SiO2, TiO2…)
2 to 4 hr2 to 4 hrHNO3
•Extremely time consuming•Extremely time consuming
Low analytical accuracy Low analytical accuracy
82
Advantages over hot plate acid digestion
Advantages over hot plate acid digestion
• Easy to use• Easy to use
High analytical accuracyHigh analytical accuracy
• Complete dissolution of the sample
• Complete dissolution of the sample
• Quick dissolution of the sample
• Quick dissolution of the sample
Time savingsTime savings
Money savingsMoney savings
12 to 20x 12 to 20x FasterFaster
12 to 20x 12 to 20x FasterFaster
83
Typical Solution Fusion Procedure – Step 1
Typical Solution Fusion Procedure – Step 1
Weigh into crucible 1.0 g LiM borate fluxWeigh into crucible 1.0 g LiM borate flux
Add 0.15 g sample ground to -200 mesh.Add 0.15 g sample ground to -200 mesh.
Add 0.20 g iodide or bromide on topAdd 0.20 g iodide or bromide on top
Heat at 1000°C while agitatingHeat at 1000°C while agitating
Rotate crucibleon inclineRotate crucibleon incline
Acid
Typical SolutionFusion Procedure – Step 2
Typical SolutionFusion Procedure – Step 2
85
Claisse model “M4”Automatic Fusion Machine
86
• High purity: 99.9+% and 99.99%
• Low hygroscopicity: H2O < 0,05%
• Controlled particle size: 100% < 500 m
• High fluidity and density
• Can include non-wetting agent
• High purity: 99.9+% and 99.99%
• Low hygroscopicity: H2O < 0,05%
• Controlled particle size: 100% < 500 m
• High fluidity and density
• Can include non-wetting agent
Claisse FluxesClaisse Fluxes
87
• 95%Pt - 5%Au
•Rigorous quality control
•Enhanced mixing features
•Scrap precious metals buying plan
• 95%Pt - 5%Au
•Rigorous quality control
•Enhanced mixing features
•Scrap precious metals buying plan
Claisse PlatinumwareClaisse Platinumware
88
PROBLEMS WITH FLUXES?
BLANK? CLEANLINESS OF FLUX MATERIAL?CLEAN UP SOLID?
RESULTING SOLN HAS HIGH DISSOLVED SOLIDS!
FLUX MATRIX INTRODUCES INTERFERING ELEMENTS?
89
NEW DEVELOPMENTS IN DISSOLUTION OF SAMPLES FOR INORGANIC ANALYSIS
1. TETRAMETHYLAMMONIUM HYDROXIDE (CH3)4NOH TMAH
DIGEST WHOLE BLOOD AT ROOM TEMP.!QUICK, SIMPLE, HIGH PURITY, LOW BLANK
90
Table II. Analysis of Certified Whole-Blood Sample
Analyte InternalStandard
Meas. Conc.(µg/L)
Expected(µg/L)
Dil. FactorConc. (µg/L)
SamplePreparation
Arsenic Ge 46.4 50 50 nitric
Arsenic Ge 93.3 100 50 nitric
Arsenic Ge 143 130-195 50 nitric
Arsenic Ge 22 17-26 50 nitric
Cadmium Rh 21 18-22 50 TMAH
Lead Tb 94 92-125 50 TMAH
Lead Tb 270 254-343 50 TMAH
Lead Tb 170 170-240 50 TMAH
Mercury Tb 10 10 50 TMAH
Mercury Tb 41 50 50 TMAH
Mercury Tm 20.2 22 20 nitric
Mercury Tm 9.6 10 20 nitric
Mercury Tm 5.9 6 20 nitric
91
92
TMAH BLANK
93
Wafer Surface Preparation by VPDVapor Phase Decomposition
Wafer Surface Preparation by VPDVapor Phase Decomposition
• native oxide layer SiO2
• dissolving the native oxide layer
• soluble contaminants in fluorosilicic acid
• integral wafer contamination can be collected in one droplet
Si Wafer Analysis
94
Wafer Preparation by VPD (1,2)Wafer Preparation by VPD (1,2)
Gaseous HF to SiO2 Deposition of HF(aq) film
a) b)
95
Wafer Preparation by VPD (3,4)Wafer Preparation by VPD (3,4)
Etching of SiO2 Surface Scan for Collecting Contaminants
c) d)
96
Wafer Preparation by VPD (5,6)Wafer Preparation by VPD (5,6)
e) f)
adding scanning solutionand surface scan
collection of contaminantsin one droplettransfer of droplet to ICP-MS
97
VPD Calibration CurvesMCN-6000 PFA-50 ELEMENT
23Na (LR) Al (MR)
Al (LR) 44Ca (MR)
184W 48Ti
98
Organic analysis usually involves extraction assample preparation step
Liquid -Liquid Extraction
Aliquot of organic solvent injected into GC
Remaining org. solvent now is itself waste!
mixorg
aq.+analyte
org.+analyte
aq
99
Solid phase extraction (SPE)N. J. K. Simpson, SPE Principles, Techniques & Applications, Marcel Dekker, 2000.
Analyte sticks to membrane,rinse out with small volumeof org. solvent.
*Much less org. waste generated than l-l extraction!*Vary chemistry of membrane, add complexing agents to sample, etc.*Eluting solvent (MeOH) can be miscible w. orig. sample (H2O)!
aq + analytethru
resin in membrane
100
Simpson, p. 5.
101
102
103
SOLID PHASE MICROEXTRACTION
SOLID PHASE EXT. FROM WATER
104
SOLID PHASE EXT. FROM WATER
105
SPE
STAT PHASE = SILICA + BONDED ORG PHASE (C18) POROUS POLYMER, XAD RESIN CARBON, POROUS GRAPHITIC CARBON
SOMETIMES DERIVATIZE, e.g., ION EXCHANGE SITES
SMALL STAT. PARTICLES, RAPID EQUILIBRATION, MULTIPLE EQUILIBRATIONS, EFFICIENT REMOVAL OF ANALYTE
n EQUILIBRATIONS
n1 D
1 ext.not fraction f
V
V K coeff. dist. D
aq 1,
org 2,d
* n much larger than LLE!
106
SPE
USUALLY ADD AQUEOUS SAMPLEELUTE WITH SMALL VOLUMEOF ORGANIC SOLVENT
CF = CONC. FACTOR = Vsample/Veluent
MUCH HIGHER CONC. FACTORSTHAN LLE
LESS ORG. SOLVENT WASTE
107
SPE IN “FILTER DISKS”
polymermembrane
Stat phase beadsimpregnated intomembrane
SHORT BED HEIGHT, 0.5 mmSMALLER PARTICLES THAN PACKED BED < 5 m, LOW BACKPRESSURESMALL Veluent, HIGH CONC. FACTORFAST, EFFICIENT
108
109
PURGE & TRAP RECOVERY = ?
110
EXTRACT INTACT COMPS. FROM SOLIDS?
SOXHLET EXTRACTION
PRESSURIZED FLUID EXT.
MICROWAVE EXTRACTION
SOFTER THAN TOTAL DISSOLUTION
Microwaves
Temp. probe
SampleSolvent