SAMPLING AND SAMPLE PREPARATION

1. SAMPLING AND SAMPLE PREPARATION

2. DEFINITION OF PROBLEM Information gathering Select analytical technique or method Implement analysis of known sample and unknowns Reduce data, interpret and report results SOLUTION TO PROBLEM

3. Important information to provide the analyst: What is the sample? What other components are present? What is the concentration range of the species to be determined? What degree of accuracy is required? How many samples are to be analysed?

4. Sample composition (can do qualitative analysis): - needed to select method for analysis - aware of: interferences, may need separations, method/solvent for dissolution, pre-treatment e.g. drying hygroscopic samples • Concentration range: • needed to select technique/method for analysis • for very low concentrations of analyte  guard against contamination from reagents/apparatus Degree of accuracy - needed to select technique/method for analysis - bear in mind: time and cost vs accuracy No. of samples: - could determine approach - important for planning

5. PROFFESIONAL ANALYTICAL CHEMISTS IN INDUSTRY ANALYTICAL CHEMISTS CHEMISTS ENGINEERS LIFE SCIENTISTS TECH. REPRESENTATIVE IN FIELD CLASSICAL APPROACH COLLECTION OF DATA/ DATA INTERPRETATIONS ABOUT PROBLEM SOLUTION TO PROBLEM

6. Remember: A chemical analysis is generally performed on only a fraction of the material. • This fraction must represent the bulk material For solids: Produce a powder that is representative of the bulk

7. Iron ore sample – showing banded iron formation Which part of this sample would you analyse?

8. Sampling Core drills + cores

9. Ice sampling Water sampling

10. Sample preparation  to produce representative samples: Crushing: Jaw crusher Vertical shaft impactor

11. Grinding and milling: Ball Mill Pestle and mortar

12. Mixing: Mixing wheel Rollers

13. Considerations during crushing and grinding: • Composition of sample may change: • loss of volatile components due to heat generated • change is water content • increased surface area to react with the atmosphere e.g. Fe2+oxidised to Fe3+ • Differences in hardness of components: • different size particles • losses due to dust • separation of components Contamination from crushers/mills due to abrasion

14. STATISTICS OF SAMPLING A chemical analysis can only be as meaningful as the sample! Sampling – process of collecting a representativesample for analysis OVERALL VARIANCE = ANALYTICAL VARIANCE + SAMPLING VARIANCE

15. Consider a powder mixture containing nA particles of type A and nBparticles type B. Probability of drawing A: p = Probability of drawing B: q = nA nA+ nB nB = 1 - p nA+ nB Where does the sampling variance come from? If n particles are randomly drawn, the expected number of A particles will be np and standard deviation of many drawings will be:

16. How many samples/replicates to analyse? Rearranging Student’s t equation: Required number of replicate analyses: e µ = true population mean x = measured mean n = number of samples needed ss2 = variance of the sampling operation e = sought-for uncertainty Since degrees of freedom is not known at this stage, the value of t for n → ∞ is used to estimate n. The process is then repeated a few times until a constant value for n is found.

17. Example: In analysing a lot with random sample variation, there is a sampling deviation of 5%. Assuming negligible error in the analytical procedure, how many samples must be analysed to give 90% confidence that the error in the mean is within 4% of the true value? For 90% confidence: t =

18. SAMPLE STORAGE Not only is the sampling and sample preparation important, but the sample storage is also critical. + LABELLING!!!

19. The composition of the sample may change with time due to, for example, the following: • reaction with air • reaction with light • absorption of moisture • interaction with the container Glass is a notorious ion exchanger which can alter the concentration of trace ions in solution. Thus plastic (e.g. PPE = polypropylene or PTFE = Teflon) containers are frequently used. Ensure all containers are clean to prevent contamination.

20. MOISTURE IN SAMPLES Moisture may be: a contaminant or chemically bound in the sample e.g. adsorbed onto surface e.g. water of crystallisation BaCl2·2H2O Varies with temperature, humidity and state of division • Accounted for by:

21. DISSOLVING SAMPLES FOR ANALYSIS Most analytical techniques require that the samples first be dissolve before analysis. It is important that the entire sample is dissolved, else some of the analyte may still be in the undissolved portion. • We will consider: • Acid dissolution / digestion • Fusion • Wet ashing • Dry ashing Inorganic samples Organic samples

22. ACID DISSOLUTION Acids commonly used for dissolving inorganic materials: Non-oxidising acids – HCl, HF, dilute HClO4, dilute H2SO4, H3PO4 Oxidising acids – HNO3, hot concentrated HClO4, hot concentrated H2SO4 A mixture of acids maybe required, e.g.: Aqua regia = HCl:HNO3 = 3:1 HCl + HClO4 HNO3 + HClO4 + HF

23. Note: Hot concentrated HClO4 is a very strong oxidant! It reacts violently with organic substances. Evaporate samples containing organic substances with HNO3 to dryness first (a few time if necessary) before adding HClO4. If the solution turns a dark colour when HClO4 is added, remove from heat and add sufficient HNO3 to the solution …AND RUN!!!!!

24. NOTE: • Hydrofluoric acid is extremely corrosive and a contact poison. Handled with extreme care!!! • Symptoms of exposure to HF may not be immediately evident. • HF interferes with nerve function and burns may not initially be painful. Accidental exposures can go unnoticed, delaying treatment and increasing the extent and seriousness of the injury. • HF penetrates tissue quickly and is known to etch bone • HF can be absorbed into blood through skin and react with blood calcium, causing cardiac arrest. HF exposure is often treated with calcium gluconate, a source of Ca2+ that sequesters the fluoride ions.

25. Further Notes Vessels for acid digestion manufactured from glass, Teflon, platinum, polyethylene Do NOT use HF in glass To prevent loss of volatile species – use teflon-lined bombs (sealed container) Bombs are frequently manufactured for use in a microwave oven

26. Fusion = melting FUSIONS To dissolve refractory substances Dissolve sample in hot molten inorganic flux. ~10 times more flux than sample (by mass) Heat crucible to 300 – 1200oC Crucibles e.g. platinum, gold, nickel, zirconium Automated fusion apparatus

27. Common fluxes used: Basic fluxes – Na2O2, Na2CO3, LiBO2,NaOH, KOH  for dissolving acidic oxides of Si and P Acidic fluxes – Li2B4O7, Na2B4O7, K2S2O7, B2O3  for dissolving basic oxides of Grp I and II metals, lanthanides and Al Then dissolve in diluted acid solution. Disadvantages of fusions: Large concentration of flux contamination Loss of volatile substances Large salt content in solution when dissolved

28. ASHING Oxidative treatment of organic samples: C converted to CO2 and H converted to H2O Problem: loss of volatile species Wet Ashing = decomposition of organic samples using strong oxidising agents e.g. H2SO4 + HNO3 HClO4 + HNO3

29. Dry Ashing = decomposition of organic samples by strong heating The solid residue is then dissolved and analysed. Not the most reliable procedure