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How can the concentration of a metal ion be measured from the light it absorbs or emits?

Explain the principles of atomic absorption spectroscopy (AAS) and atomic emission spectroscopy, and their use in determining trace metal concentrations.

How AAS and atomic emission measure trace metals: electron transitions, element-specific wavelengths, the calibration-curve method and Beer-Lambert relationship, with worked SACE-style concentration-from-absorbance calculations.

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  1. What this dot point is asking
  2. Lead worked calculation
  3. How AAS works
  4. How atomic emission works
  5. The calibration-curve method
  6. Strengths and limits
  7. Why it matters for monitoring

What this dot point is asking

SACE expects you to explain the electron transitions behind both techniques, why each is element-specific, and how a calibration curve converts an absorbance reading into a concentration.

Lead worked calculation

How AAS works

The absorbed wavelengths are set by the energy gap ΔE\Delta E between levels, related to wavelength by E=hcλE = \dfrac{hc}{\lambda}. Because each element has unique energy gaps, the absorbed wavelengths are a fingerprint, which is why a lamp made of the specific element is required and why other metals in the sample do not interfere at that wavelength.

How atomic emission works

In atomic emission, the flame or plasma supplies enough energy to excite electrons to higher levels. As they fall back, they emit photons of characteristic wavelengths: atomatom+photon\text{atom}^* \rightarrow \text{atom} + \text{photon}. The emitted colours identify the element (the basis of the flame test: sodium yellow, potassium lilac, copper green-blue), and the emission intensity is proportional to concentration. AAS measures light removed; emission measures light given out. AAS is generally better for trace levels because measuring a small decrease against a bright source is more sensitive than detecting faint emission.

The calibration-curve method

The standard procedure: prepare a series of standards spanning the expected range, measure each, plot the calibration curve, then read the unknown off the linear portion. Reasons this works: the line passes through the origin (zero concentration gives zero absorbance), and proportionality holds only within the linear range, so very concentrated samples must be diluted back into range.

Strengths and limits

AAS detects metals at parts-per-million and parts-per-billion levels, far below what titration can reach, making it ideal for trace contaminants such as lead, cadmium and mercury in water. Its main limitations are that it measures one element at a time (one lamp per element), needs matrix-matched standards, and loses proportionality above the linear range.

Why it matters for monitoring

AAS and atomic emission are the workhorses of trace-metal monitoring, quantifying toxic metals in drinking water, soil and biological samples at concentrations far too low for titration. Their element specificity lets analysts target a single contaminant in a complex environmental sample.

Exam-style practice questions

Practice questions written in the style of SACE Board exam questions on this dot point, with worked answer explainers. The year tag is the paper they imitate, not the source.

SACE 20224 marksStandard lead solutions gave the following AAS absorbances: 2.0 ppm0.1102.0\ \text{ppm} \rightarrow 0.110; 4.0 ppm0.2204.0\ \text{ppm} \rightarrow 0.220; 6.0 ppm0.3306.0\ \text{ppm} \rightarrow 0.330; 8.0 ppm0.4408.0\ \text{ppm} \rightarrow 0.440. A water sample gave an absorbance of 0.2750.275. Using the calibration data, determine the concentration of lead in the sample and state one assumption you make.
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Step 1: the standards show a straight line through the origin; the gradient is 0.1102.0=0.0550 absorbance per ppm\dfrac{0.110}{2.0} = 0.0550\ \text{absorbance per ppm}. (2 marks)

Step 2: rearranging A=(gradient)×cA = (\text{gradient}) \times c, c=Agradient=0.2750.0550=5.0 ppmc = \dfrac{A}{\text{gradient}} = \dfrac{0.275}{0.0550} = 5.0\ \text{ppm}. (1 mark)

Assumption: the sample lies within the linear (calibration) range and the matrix of the sample matches the standards so that absorbance is directly proportional to concentration. (1 mark)

SACE 20203 marksExplain why atomic absorption spectroscopy is specific for a single element, and why a different lamp is required to measure a different metal. Refer to electron transitions in your answer.
Show worked answer →

Each element has a unique set of electron energy levels, so the energy gaps between levels, and therefore the wavelengths of light its atoms absorb, are characteristic of that element alone. (1 mark)

In AAS the source is a hollow-cathode lamp made of the element being measured; it emits light at exactly the wavelengths that element's atoms can absorb, when an electron is promoted from the ground state to a higher level: atom+photonatom\text{atom} + \text{photon} \rightarrow \text{atom}^*. (1 mark)

Because another metal absorbs at different wavelengths matched to its own energy gaps, its atoms would not absorb the first lamp's light, so a lamp made of the new element is needed. This element-specific source is what makes AAS selective. (1 mark)

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