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Calibration · No. 18Gravimetry Under the Standards

Calibration — the standards themselves

Gravimetry under the standards

A calibration curve is only as true as the standards behind it. Weigh what you put in, correct for what it really is, and calculate the concentration you actually made.

By Medrado Analytical Innovations · Foundations, No. 18 · for the working analyst

In this piece · 9 min read
  1. The one-line idea
  2. The label is not the value
  3. Which purity, and when it is already done
  4. Weigh where weighing is honest
  5. By mass or by volume
  6. Calculate what you made, then carry it through
  7. How you know it worked
  8. The judgement

Every calibration curve rests on a column of numbers nobody looks at twice: the concentrations of the standards. They are typed in once, usually straight off the bottle (10, 50, 100 mg/L), and from then on every result the instrument reports is measured against them. If those numbers are a little wrong, the curve is a little wrong in exactly the same way, at every level, and nothing in the fit will tell you. A curve can only be as true as the standards behind it. This piece is about making those standards true: weighing what you put in, correcting for what it really is, and calculating the concentration you actually made instead of the one you meant to make. (Here the solid or neat material is weighed and the solution is made up to volume; preparing the whole solution by mass is covered further down.)

The one-line idea

A standard's concentration is not a label. It is a calculation from three measured things: how much you weighed, how pure it was, and how much solution you made.

C (mg/L) = m (mg) × P / V (L) m = mass weighed, P = purity as a mass fraction, V = final volume each dilution: C_new = C_old × V_aliquot / V_flask

Every term carries its own uncertainty, and the worked example in the Eurachem/CITAC guide shows how they combine. For a cadmium standard made from 100.28 mg of high-purity metal (standard uncertainty 0.05 mg), of purity 0.9999 (u = 0.000058), made up to 100.0 mL, which is 0.1000 L (u = 0.07 mL), the result is 100.28 mg × 0.9999 / 0.1000 L = 1002.7 mg/L, with a combined standard uncertainty of 0.9 mg/L as the guide gives it.1 Two things to notice. The true value is 1002.7, not the 1000 on the label. And in that example, a high-purity metal, purity barely matters: the relative uncertainties are about 0.07% for the volume, 0.05% for the mass and 0.006% for the purity. For a 98%-pure organic compound with a purity uncertainty of half a percent, purity would dominate instead.

Check yourself

Answer in your head first, then open the answer. Any question can go into your Quiz me.

  1. What is a standard's concentration?

    Show the answer
    “A standard's concentration is not a label.”

    See it in the article ·

  2. A bottle labelled 100 mg/L has a certificate value of 98 mg/L. What do you enter for that calibration point?

    Show the answer
    “The correct default is to enter the certified, purity-corrected concentration as the value of every calibration point”

    See it in the article ·

  3. What kind of purity does the concentration calculation need?

    Show the answer
    “The calculation above needs purity as a mass fraction”

    See it in the article ·

Glossary

Purity (mass fraction)
Grams of the compound per gram of the material weighed; the basis a concentration calculation needs.
Minimum weight
The smallest net weight a balance can honestly weigh; under USP <41>, 2000 times its repeatability standard deviation.
Air buoyancy correction
The small correction for air pushing up on what you weigh; about +0.1% for water.
Tolerance
The largest error a piece of glassware is allowed, not its standard uncertainty.

Sources

  1. Eurachem/CITAC Guide, Quantifying Uncertainty in Analytical Measurement, 3rd ed. (QUAM:2012.P1), Example A1: Preparation of a calibration standard.
  2. Certificates of analysis for pure-substance certified reference materials, e.g. NMIJ (AIST) CRM certificates (purity stated as a mass fraction with an expanded uncertainty).
  3. S. Westwood et al., "Methods for the SI-traceable value assignment of the purity of organic compounds (IUPAC Technical Report)", Pure Appl. Chem. 95(1), 1–77 (2023), doi:10.1515/pac-2020-0804.
  4. Restek, "Are your reference standards weight-corrected for purity?" (technical FAQ, discover.restek.com).
  5. USP General Chapter ⟨41⟩ Balances (current USP–NF).
  6. NIST, SOP 2: Recommended Standard Operating Procedure for Applying Air Buoyancy Corrections (NISTIR 6969).
  7. ASTM E288 (current edition), Standard Specification for Laboratory Glass Volumetric Flasks (Class A tolerances); ISO 1042, Laboratory glassware: one-mark volumetric flasks.
  8. ASTM D4307-17(2021), Standard Practice for Preparation of Liquid Blends for Use as Analytical Standards.