Prepare, Standardise And Use Solutions

Prepare, Standardise And Use Solutions

First step • Review test request and identify samples to be tested, • Select a method and equipment and instruments involved • All methods should be recorded in a book of standard methods • Standard methods must be verified as correct • Methods can be purchased or copied from nation or international organisation approved by NATA

National Association of Testing Authorities • NATA is the authority that provides independent assurance of technical competence through a proven network of best practice industry experts for customers who require confidence in the delivery of their products and services. • NATA provides assessment, accreditation and training services to laboratories and technical facilities throughout Australia and internationally. • NATA ACCREDITATION provides a means of determining, formally recognising and promoting the competence of facilities to perform specific types of testing, inspection, calibration, and other related activities

Test methods • Australian standard methods • EgAS/NZS 2341.2:2015 • Methods of testing bitumen and related roadmaking products - Determination of dynamic viscosity by vacuum capillary viscometer • AS/NZS 2891.14.1.1:2013 Methods of sampling and testing asphalt - Field density tests - Determination of field density of compacted asphalt using a nuclear surface moisture-density gauge - Direct transmission mode

Test Methods • British Standards • E.g. BS 7671:2008+A3:2015, • Requirements for Electrical Installations. IET Wiring Regulations. • BS ISO 12154:2014 • Determination of density by volumetric displacement. Skeletondensity by gas pycnometry

Test Methods • ISO (International Organization for Standardization) • E.g. ISO 565:1990 • Test sieves -- Metal wire cloth, perforated metal plate and electroformed sheet -- Nominal sizes of openings

Testing Methods • American Organization of Analytical Chemists International (AOAC International) • Official Methods of Analysis of AOAC INTERNATIONAL • E.g. AOCS Official Method Aa 4-38Oil • DEFINITIONThis method determines the substances extracted by petroleum ether under conditions of the test

Testing Methods • In House Methods • 1) Prepared by your own laboratory when it is not possible to find a suitable method with AustStds , BSI or AOAC. • 2) Customers standard method • Sometimes the customer request the use of their particular company methods

Volumetric Analysis: Acid-Base titration Titration - is the measurement of the volume of a standard solution required to completely react with a measured volume or mass of substance being analyzed (also referred to as analyte) Standard solution - is a solution containing a known concentration of solute. Standardization - the concentration of a solution is determined by using it to titrate a carefully measured quantity of a primary standard. Primary standard - is a highly purified compound that serves as a reference material in all volumetric and mass titrimetric methods. (high purity, stable toward air/dried, absence of hydrated waters, cost, soluble in solvent, large molar mass)

Secondary standard solution - titrant that is standardized against a standard solution. Indicators - are added to analyte solution in order to give an observable physical change (end point) at or near the equivalence point. Typically appearance or disappearance of color, change in color, ppt formed, etc. Equivalence point - is reached when the amount of added titrant is chemically equivalent to the amount of analyte in sample. End point - physical change that can be observed associated with the conditions of equivalence. Titration error - difference in volume or mass between the equivalence point and the end point.

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Preparing Standard Acid Solutions • Hydrochloric acid is widely used for titration of bases. • Dilute solutions of HCl are stable indefinitely and do not cause troublesome precipitation reactions with most cations. • Solutions of perchloric acid and sulfuric acid are also stable and are useful for titrations where chloride ion interferes by forming precipitates. • Standard solutions of nitric acid are seldom encountered because of their oxidizing properties. • Standard acid solutions are ordinarily prepared by diluting an approximate volume of the concentrated reagent and subsequently standardizing the diluted solution against a primary-standard base.

Standardizing Acids • Acids are frequently standardized against weighed quantities of sodium carbonate. • Tris-(hydroxymethyl)aminomethane, (HOCH2)3CNH2, known also as TRIS or THAM, is available in primary-standard purity from commercial sources. (HOCH2)3CNH2 + H3O+ (HOCH2)3CNH3++ H2O • Sodium tetraboratedecahydrate (Na2B4O7.10H2O) has also been recommended as primary standards. The reaction of an acid with the tetraborate is B4O72- + 2H3O+ + 3H2O 4H3BO3

Preparing Standard Base Solutions • Sodium hydroxide is the most common base for preparing standard solution, although potassium hydroxide and barium hydroxide are also encountered. • None of these is obtainable in primary-standard purity, so standardization is required after preparation. The Effect of Carbon Dioxide • In solution as well as in the solid state, the hydroxides of sodium, potassium, and barium react rapidly with atmospheric carbon dioxide to produce the corresponding carbonate: CO2 + 2OH- CO32- + H2O

Standardizing Solutions of Bases • Several excellent primary standards are available for the standardization of bases. • Potassium hydrogen phthalate (KHC8H4O4) is an ideal primary standard. • It is a nonhygroscopic crystalline solid with a high molar mass (204.2 g/mol). • For most purposes, the commercial analytical-grade salt can be used without further purification.

Standardizing Solutions of Bases • Benzoic acid is obtainable in primary-standard purity and can be used for the standardization of bases. • Potassium hydrogen iodate, KH(IO3)2, is an excellent primary standard with a high molecular mass per mole of protons.

Testing Methods • Methods Must be tested against standards to determine if the method is accurate • All equipment must be calibrated • All Method testing and calibrations must be done with Certified Reference Materials

Measurement traceability (2) The Sample Analysed by Secondary method: e.g. lab. method Calibrated by Primary methods (often gravimetric) e.g. AOAC, EPA Calibration Standards Method routinely checked by Certified by analysis Secondary RMs In-house QC materials (fairly cheap, larger amounts, matrix matched, short life) Certified Reference Materials (CRMs - expensive, small amounts, best accuracy, long life) Periodically checked

Reference materials & check samples SAMPLES SUPPLIED FOR PROFICIENCY TESTING INTERNAL QC SAMPLES Internal QC samples are prepared and quantity values of target components are checked against CRMs An accredited laboratory has to prove its performance by routinely analysing samples supplied by an independent laboratory CERTIFIED REFERENCE MATERIALS (CRMs)

Standard Operating Procedures (SOP) • In addition to methods there are SOPs that must be followed: • Receiving of Samples • Register of samples • History of sample • Storage of samples • Reporting of Results • Storage of results • Validation of Staff re each method • Calibration

Lab. No. F7-002 Keeping track of the samples • Sample registration gives each sample a unique lab number. • The sample register records all the information about the sample. • Just like a sample’s passport, you should not confuse any sample with any other. • The history of the sample should be traceable throughout. Sample integrity Samples recorded on receipt

Part 1 - The Importance of Analysis and Appreciation of Error Contents: • Introduction to the importance of analytical information (slides 3&4) • Appreciating, managing and understanding error (slide 5) • The Analytical Process (slides 6-16) • Sampling strategies (slides 17-26) The presentation contains some animation which will be activated automatically (no more than a 2 second delay), by mouse click or by use of the ‘page down’ key on your keyboard.

Why is Analytical Science so Important? Analytical Science truly is an inter-disciplinary science, being essential not only in Chemistry, but in the Bio-sciences, Geo-sciences Environmental and Forensic Sciences, Agriculture, Medicine as well as Engineering and Manufacturing Technologies. It is the means by which measurements (both qualitative and quantitative) are made. It is essential that the data obtained is accurate, so that the decisions made which are based upon that data are correct and appropriate.

Health & safety -identification of fibres Agriculture e.g. Pesticide residue analysis Chemical plant Environmental monitoring of effluent Explanation of the images Forensic science Pharmaceutical analysis Materials science Analysis of foods

Appreciating, Managing and Understanding Error The image on the left shows a police speed camera. How accurate is the speed measured and recorded by the camera? Also, how accurate is the speedometer of the car caught speeding? To allow for both of these unknowns, motorists are rarely prosecuted for speeds not in excess of 10% of the road limit. Thus, an allowance is being made for the potential inaccuracy of the data. All analytical data has a measure of inaccuracy and it up to the Analytical Scientist to be aware of this and to be able to express this, if necessary, in quantitative terms. Measurements produced within a Quality Assured environment are more likely to be accurate and reliable than those produced from laboratories operating outside the principles of quality assurance.

The Analytical Process Consists of seven unit processes 1 2 3 4 5 6 7 1. Consider the problem and decide on the objectives 2. Select procedure to achieve objectives 3. Sampling 4. Sample preparation 5. Separation and/or concentration 6. Measurement of target analytes 7. Evaluation of the data, have the objectives been met? Now you can look at these in a little more detail.

Consider the problem and decide on the objectives 1 2 3 4 5 6 7 • Analyses cost money and should only be carried out for a specific reason • The Analytical Scientist in conjunction with the client or sample provider, • need to agree the overall objectives for the analysis • The Analytical Scientist will often be proactive by designing analysis systems • which may help to improve the quality of a product and/or reduce the cost of • production.

Select procedure to achieve objectives 1 2 3 4 5 6 7 • The Analytical Scientist can use many technologies to provide analytical • information to achieve the objectives. The choice should focus on: • expected level(s) of analyte(s) • precision and accuracy required • sample matrix and likely interferences • number of samples to be analysed

Sampling Sampling of dried banana leaves 1 2 3 4 5 6 7 • Most important stage in the analytical process and that likely to • produce the highest proportion of the total error in any analysis • Samples where appropriate should be representative of the bulk from • which they were removed • Once the sample has been taken, it should retain it’s ‘integrity’ (not alter • it’s structure or lose components) until the analysis has been carried out

Sample preparation Microwave digestion oven for trace metal analysis 1 2 3 4 5 6 7 • Most samples requiring analysis need to be transformed physically or • chemically from one form to another • Sample preparation may involve: • simple dissolution in aqueous or organic solvents • treatment with dilute acids and bases • digestion with hot concentrated acids (oxidation) • treatment with molten fluxes at temperatures of up to 1400oC

Separation and/or concentration Soxflo extraction 1 2 3 4 5 6 7 • Most samples for analysis are complex and could contain other components • which might interfere with the final analytical measurement • Many of the analyte levels that need to be determined are below the levels • of detection of the equipment available - thus concentration is required • The technologies used to perform both separation and concentration are • frequently the same (solvent extraction, chromatography, eletrophoresis etc)

Measurement of target analytes GC/MS spectrometer 1 2 3 4 5 6 7 • This is the unit process where measurement is finally made • The technique used may be based upon either chemical or physical • principles, the most important are based upon the principles of: • classical analysis (eg: volumetric and gravimetic analysis) • chromatography (eg; glc, hplc) • spectroscopy (eg: molecular and atomic techniques)

Evaluation of data - have the objectives been met? 1 2 3 4 5 6 7 • Application of statistical techniques to maximise reliability of the data • Quantitative results to be accompanied by estimate of measurement • uncertainty • Decision as to whether or not the analysis carried out has satisfied the • objectives. If not, then consider what additional tests/analyses need • to be carried out

In this image, dried banana leaves are being sampled prior to analysis for total nitrogen. The leaves are first cut roughly before transferring to a ‘coffee grinder’ in order to obtain a representative sample. Dried banana leaves Coffee grinder Explanation of images Digestion vessel Expansion vessel to avoid explosions This image shows a commercial microwave oven for digesting organic matter prior to analysis for trace metallic components. The vessels contain the samples together with oxidative acids (eg. HNO3) and the digestion occurs at high temperatures and pressures.

The image shows a Soxflo extractor being used to extract oil from rape seed. This extraction method is a safer alternative to the traditional Soxhlet extraction Explanation of images Mass spectrometer The image shows a typical gcms (gas chromatograph/mass spectrometer. The components of the mixture separated by the gc can be both uniquely identified and quantified by the spectrometer. Gas chromatograph

The analytical process - error components 1 2 3 4 5 6 7 Practical stages Important to realise that error will arise in all of these practical stages in the process, with maximum error components likely to occur within the sampling (3) and the sample preparation(4) stages

Sampling - the lynchpin of the analysis Of all of the stages in the analysis, the taking of the sample is the most important. This is because, the sample eventually analysed will be a very small part of the bulk material to which it is assumed to relate and from which decisions of a commercial or a technological nature will be made. Samples must therefore be representative. Definition of a representative sample: A portion of a material taken from a consignment and selected in such a way that it possesses all of the essential characteristics of the bulk. EXAMPLE Consider an Import company to which a consignment of low grade Chromium ore has been delivered. They have agreed with the supplier that they will pay for the Ore based upon its Chromium content. Samples of the Ore are taken from the consignment, but due to lax sampling practice, the samples taken are not representative. The resultant analysis gives a Chromium abundance of 5% by weight when in fact, on average, the Chromium abundance is approximately 4%. Thus the Import company pays about 25% above the value of the goods purchased.

Smoking machine to identify & quantify compounds in tobacco smoke Sampling procedures The diagram illustrates the situation where a consignment consists of a number of separate sampling units. Increments are taken from each of these units to produce a gross sample. This is homogenised and sub-sampled followed by further sub-sampling, finally producing samples for analysis. At each stage sampling must be representative and at each stage further error is introduced. Increment Sampling unit Gross/composite sample Sub-sample Further sub-sample Replicate samples for analysis

Sampling continued -liquids (1) Errors occur in sampling operations, due to the inherent heterogeneity of bulk matrices. Single phase liquids, following shaking or mixing, are likely to be homogeneous and thus a single sample should be sufficient for analysis. However, where you have a depth of liquid (eg: a drum or an ocean even), it is not possible to assume that the liquid at the top is of the same consistency as that down the column of liquid and thus a single sample is no longer suitable. Sample is being taken away from the side of a ship to avoid metal contamination from the hull. Sample being abstracted from about 1m depth to avoid the surface layer in which insoluble organics can accumulate

Sampling continued - liquids (2) Liquids flowing in confined boundaries (eg: pipes, rivers and canals) are subject to principles of laminar flow and as such the liquid flows faster in the centre, with almost zero flow at the edge of the pipe or the bank of the river/canal. Huddersfield Narrow Canal This waterway is slow-flowing (no turbulence or mixing), samples should be taken across the width of the canal. Turbulent flow When sampling from pipes, turbulent flow can be created by introducing a right angled bend into the pipe, with sampling just before the flow returns to laminar conditions. Sampling point Laminar flow Liquid flowing in a pipe

Sampling continued - solids (1) • In terms of potential heterogeneity, the sampling of solid matrices poses a major problem. Following extensive grinding and mixing, solids can still exhibit some heterogeneity and thus introduce errors into any analysis. Typical examples of solid sampling situations are: • pharmaceuticals (tablets & powders) • minerals • contaminated land surveys • agricultural products (e.g:seeds, • grains, leaves)

Sampling continued - solids (2) ‘GRAB’ Sample of sediment taken from the bottom of the North Sea. The sample is air dried before discarding any large stones etc. The remaining sample is then sub-sampled to reduce the quantity before being ground, sieved and then stored in clean containers prior to analysis Grain silo - take samples for analysis when the silo is emptied Derelict industrial site which may require a contaminated land survey prior to redevelopment dependent upon previous usage. Concrete samples taken as ‘cores’

Sampling continued - statistical sampling Because of the inherent heterogeneity of solid matrices, the process of ‘Statistical Sampling’ is often employed. This is based on the principle that all particles or portions of the population (material to be sampled) have an equal probability of being present in the sample that is taken. This is best illustrated by considering the sampling of a potentially contaminated piece of land where contamination may be concentrated in small areas of the overall land mass. Given that the cost of the survey, the number of samples taken and the potential accuracy of the result are all interrelated, a compromise is normally adopted whereby the sampling sites are chosen randomly within some strict guidelines Divided into smaller imaginary plots Samples ( ) taken from random plots or randomly from each plot. Samples combined (composited) for analysis or analysed separately

Sampling continued - contaminated landfill site Suppose that the site is heavily polluted but in irregular patches. If you are not aware of the location of the patches but there is the need to reduce the average pollution concentration over the whole site to below 1%, you need a sampling strategy that shows by analysis which areas require treatment and which do not.

Contaminatedlandfill site (2) Divide the target area into a grid of sampling cells and take 3 random samples from each grid. From the analyses you can identify which of the cells are the most contaminated and treat them accordingly.

Contaminatedlandfill site (3) By cleaning up only those grid areas identified as having the highest pollutant abundance you can now calculate whether or not the target of less than 1% has been achieved. If it has not, then further clean up of the other areas can be carried out

Sampling continued - air, gases & vapours(1) Given the difficulties of taking and storing gas samples, it is recognised that gases etc. are best analysed in situ by a suitable on-line analyser. Such analysers are routinely in use by DEFRA and local councils, to monitor levels of CO, CO2, SO2 and oxides of nitrogen within the air we breathe. Many organic vapours can either be monitored on line (e.g by using dedicated IR analysers) or they may be trapped onto suitable substrates (e.g: activated charcoal or TENAX) for analysis in the laboratory. Given that it is impossible to tell whether or not the samples are homogeneous, time weighted average data is frequently quoted.

Sampling continued - air, gases & vapours(2) Data set to illustrate the reduction in NO2 emissions in the UK between, 1970-2000. Analysis for NO2 carried out by using either diffusion tube monitors or by chemiluminescence analysers Simple absorption devices used trap volatile organics (VOCs) for eventual analysis in the laboratory: diffusion tube containing Tenax tube containing activated charcoal cartridge containing C18 adsorbant

Prepare, Standardise And Use Solutions