Primary standards preparation

External Standards—The sulfur compounds and matrices of external standards should be representative of the sulfur compounds and sample matrices being analyzed. Test Methods D2622 and D3120 can be used to analyze materials for calibration of this test method. The internal standardization procedure can also be used for generating external standards. Alternatively, primary standards prepared as described in 6.1.4 can be used for method calibration when it is demonstrated that the matrix does not affect calibration. Only one external standard is necessary for calibration, provided that the system performance specification (7.3) is met. An external standard must contain at least one sulfur compound at a concentration level similar, for example, within an order of magnitude to those in samples to be analyzed. 

The majority of titrations involving basic analytes, whether conducted in aqueous or nonaqueous solvents, use HCl, HCIO4, or H2SO4 as the titrant. Solutions of these titrants are usually prepared by diluting a commercially available concentrated stock solution and are stable for extended periods of time. Since the concentrations of concentrated acids are known only approximately,the titrant s concentration is determined by standardizing against one of the primary standard weak bases listed in Table 9.7. 

Solutions of Mn04 are prepared from KMn04, which is not available as a primary standard. Aqueous solutions of permanganate are thermodynamically unstable due to its ability to oxidize water. 

Solutions of Na2S203 are prepared from the pentahydrate and must be standardized before use. Standardization is accomplished by dissolving a carefully weighed portion of the primary standard KIO3 in an acidic solution containing an excess of KI. When acidified, the reaction between 103 and K... 

National Institute of Standards and Technology (NIST). The NIST is the source of many of the standards used in chemical and physical analyses in the United States and throughout the world. The standards prepared and distributed by the NIST are used to caUbrate measurement systems and to provide a central basis for uniformity and accuracy of measurement. At present, over 1200 Standard Reference Materials (SRMs) are available and are described by the NIST (15). Included are many steels, nonferrous alloys, high purity metals, primary standards for use in volumetric analysis, microchemical standards, clinical laboratory standards, biological material certified for trace elements, environmental standards, trace element standards, ion-activity standards (for pH and ion-selective electrodes), freezing and melting point standards, colorimetry standards, optical standards, radioactivity standards, particle-size standards, and density standards. Certificates are issued with the standard reference materials showing values for the parameters that have been determined. 

Standard 1/10 N nitrite is used to titrate a solution prepared by dissolving 10—100 mg of sulfamic acid and about 6 mL of (1 + 1) H2SO4 in 300 mL of distilled water at 40—50°C. At the end point, the colorless external potassium iodide starch-paste indicator changes to blue. A 1-mL solution of 1/ION NaN02 is equivalent to 9.709 mg of sulfamic acid. The 1/10 N nitrite titrant solution is standardized using primary standard-grade sulfamic acid. For sulfamate assay determination, the same procedure is used as for sulfamic acid. 

In titrimetry certain chemicals are used frequently in defined concentrations as reference solutions. Such substances are referred to as primary standards or secondary standards. A primary standard is a compound of sufficient purity from which a standard solution can be prepared by direct weighing of a quantity of it, followed by dilution to give a defined volume of solution. The solution produced is then a primary standard solution. A primary standard should satisfy the following requirements. 

Solutions of EDTA of the following concentrations are suitable for most experimental work 0.1M, 0.05M, and 0.01 M. These contain respectively 37.224 g, 18.612g, and 3.7224 g of the dihydrate per litre of solution. As already indicated, the dry analytical grade salt cannot be regarded as a primary standard and the solution must be standardised this can be done by titration of nearly neutralised zinc chloride or zinc sulphate solution prepared from a known weight of zinc pellets, or by titration with a solution made from specially dried lead nitrate. 

The standardisation of thiosulphate solutions may be effected with potassium iodate, potassium dichromate, copper and iodine as primary standards, or with potassium permanganate or cerium)IV) sulphate as secondary standards. Owing to the volatility of iodine and the difficulty of preparation of perfectly pure iodine, this method is not a suitable one for beginners. If, however, a standard solution of iodine (see Sections 10.112 and 10.113) is available, this maybe used for the standardisation of thiosulphate solutions. 

Precipitation methods 418 Precipitation reactions 340 theory of, 340, 342, 579 Precision 13, 129 Preparation for analysis 109 solution of sample, 110 Preventive solution 368 Primary amines see Amines Primary standard substances requirements of, 261... 

In a multi-year, multi-laboratory situation it is unlikely that the amount of primary standard (PS) will suffice to cover all requests. The next best thing is to calibrate a larger amount of lower-quality secondary standard (SS) against the PS, and to repeat the calibration at specified intervals until both the PS and the SS have been consumed. In this way, consistency can be upheld until a new lot of PS has been prepared and cross-validated against the previous one. In practice, a working standard will be locally calibrated against the SS and be used for the daily method calibration runs. (See Section 4.32.)... 

Trifluoromethanesulfonates of alkyl and allylic alcohols can be prepared by reaction with trifluoromethanesulfonic anhydride in halogenated solvents in the presence of pyridine.3 Since the preparation of sulfonate esters does not disturb the C—O bond, problems of rearrangement or racemization do not arise in the ester formation step. However, sensitive sulfonate esters, such as allylic systems, may be subject to reversible ionization reactions, so appropriate precautions must be taken to ensure structural and stereochemical integrity. Tertiary alkyl sulfonates are neither as easily prepared nor as stable as those from primary and secondary alcohols. Under the standard preparative conditions, tertiary alcohols are likely to be converted to the corresponding alkene. 

The application of electroanalysis in non-aqueous media to a certain analytical problem requires a well considered selection of the solvent together with a suitable electroanalytical method, which can be carried out on the basis of the solvent classes mentioned in Table 4.3 and of the related theories. The steps to be taken include the preparation of the solvent and the apparatus for the electroanalytical method proper, together with other chemicals, especially when the method includes titration. Much detailed information on the purification of the solvents and on the preparation of titrants and primary standards can be found in the references cited in Section 4.1 and in various commercial brochures1,84,85 and books17,86-89 we shall therefore confine ourselves to some remarks on points of major importance. 

The application of PSA measurements for clinical monitoring of prostatic carcinoma requires fine tuning of PSA assays. One important aspect of this tuning is to have well-defined standards (primary calibrators). Calibrators or primary reference materials consisting of PSA complexed with ACT have been prepared and are available to sponsors of commercial immunoassays. As a result of this, some sponsors have studied calibration stability and have shown that calibration did not change within 14 to 90 days. Primary references of 90 percent PSA-ACT and 10 percent f-PS A have been shown to minimize differences in PSA measurements between different assays [NCCLS Document—Primary Reference Preparations Used to Standardize Calibration of Immunochemical Assays for Serum Prostate... 

NCCLS Document 1/L A 19-A. Primary reference preparations used to standardize calibration of immunochemical assays for serum prostate-specific antigen (PSA) Approved Guideline. NCCLS, Villanova, PA National Committee for Clinical Laboratory Standards (1996). 

The prepared NaOH solution is a secondary standard because its concentration is determined by titration against a primary standard. 

Solutions of precisely known concentration must be prepared by directly weighing the primary standard. 

This last paragraph inevitably leads to the questions, So how do we know what the exact temperature is and How do I know if my thermometer follows profile (a) or profile (b) in Figure 1.4 Usually, we do not know the answer. If we had a single thermometer whose temperature was always accurate then we could use it as a primary standard, and would simply prepare a calibrated thermometer against which all others are calibrated. 

Typically, acid soils are titrated with a sodium or calcium hydroxide [NaOH or Ca(OH)2] solution and basic soils with hydrochloric acid (HC1), and pH changes are most commonly followed using a pH meter. Carbonates in basic soils release C02 during treatment with HC1, thus making the titration more difficult. For this reason, carbonates are often determined by other methods. It is important to keep in mind that basic solutions react with carbon dioxide in air and form insoluble carbonates. This means that either the basic titrant is standardized each day before use or the solution is protected from exposure to carbon dioxide in air. Specific descriptions of titrant preparation, primary standards, and the use of indicators and pH meters in titrations can be found in Harris [1] and in Skoog et al. [2],... 

In the analysis of solid samples (e.g., LA-ICP-MS, SEM), synthetic standards cannot easily be prepared to the required concentrations, and accurate calibration of such techniques is often challenging. In some cases (e.g., SEM) pure element or single mineral standards are used, ideally with an appropriate standard for each element to be quantified. (It is possible in SEM, within limits, to use fewer standards than the number of elements to be determined, with the calibration for other elements being predicted from the response of the nearest element.) More often, however, multielement primary standards are used as the means of calibrating the instrument, e.g., for LA-ICP-MS of glasses, volcanics, and ceramics, two glass standards, NIST 610 and 612 (Pearce et al. 1996), are often used. It is always advisable to use more than one multielement standard in order to cover as wide a range of concentrations as possible, and to use at least one additional independent reference material as an unknown, for quality assurance purposes (see below). 

Primary standard A specially manufactured analytical reagent of exceptional purity for standardizing solutions and preparing reference standards. 

The alternative to the above is using an accurately weighed solid material as the known standard. Such a material is called a primary standard. Thus, a primary standard is a material that can be weighed accurately either for the purpose of preparing a standard solution (which then does not have to be standardized) or for comparison to a solution with which it reacts for the purpose of standardizing that solution. For standardization with a primary standard, Equation (4.21) becomes... 

The molarity of the EDTA solution, MEDTA in Equation (5.52), can be known directly through its preparation with the use of an analytical balance and a volumetric flask. That is, one can purchase pure disodium dihydrogen EDTA and use it as a primary standard. In that case, the solution is prepared and the concentration calculated according to the discussion in Chapter 4 (see Section 4.3, especially Example 4.2, and Section 4.4.1). 

---