These revision notes cover everything you need for AP Chemistry Topic 3.13: Beer-Lambert Law. Read through the key ideas below, then test yourself with the 18-question quiz.
Transmittance and Absorbance
A spectrophotometer shines light of one selected wavelength through a sample and compares the intensity reaching the detector with the intensity that entered. Transmittance is the fraction that gets through: T = I/I₀, a number between 0 and 1, often reported as percent transmittance, %T = 100 × I/I₀.
Absorbance is defined from transmittance by A = −log T. A sample that transmits 10% of the light has T = 0.10 and A = 1.00. A sample that transmits 1% has A = 2.00. Each absorbance unit corresponds to a tenfold drop in transmitted light, and absorbance has no units.
These two quantities behave differently, and the difference runs the whole topic. Absorbance is directly proportional to concentration and path length. Transmittance is not proportional to anything; it falls exponentially as concentration rises.
The Beer-Lambert Law
A = εlc
Absorbance equals molar absorptivity times path length times concentration. The path length l is the width of the cuvette the light passes through, in centimetres, usually 1.00 cm. The concentration c is in mol/L. The molar absorptivity ε, in L mol⁻¹ cm⁻¹, is a constant for a given substance at a given wavelength: it measures how strongly that substance absorbs at that wavelength.
Because ε and l are fixed in any one experiment, absorbance tracks concentration exactly. Double the concentration and the absorbance doubles. Double the path length and the absorbance also doubles. Triple the concentration and absorbance triples. This proportionality is what makes absorbance a measuring tool rather than just an observation.
Absorbance also explains itself at the particle level. Doubling the concentration doubles the number of absorbing particles in the light path, so twice as many photons are captured in each segment of the journey, and the absorbance rises in step.
Calibration Curves
An unknown concentration is found from a calibration curve: a plot of absorbance against concentration for a series of standard solutions of known concentration, all measured at the same wavelength in the same cuvette. The plot is a straight line through the origin, and its slope equals εl. Measuring the unknown’s absorbance and reading across to the line gives its concentration.
Two features make the measurement trustworthy. First, absorbance is measured at λ_max, the wavelength where the substance absorbs most strongly, because there a given concentration produces the largest signal and small concentration changes produce the largest absorbance changes. Second, the cuvette is first filled with a blank, the solvent with no absorbing substance, and the instrument is zeroed on it, so the absorbance recorded afterward belongs to the solute alone, not to the solvent or the cuvette walls.
A calibration line that misses the origin slightly, with a small positive intercept, points to a blank problem: something in the solvent, cuvette, or instrument offset is absorbing a little light before any solute is added.
Worked Examples
Example 1: absorbance and percent transmittance
A solution of concentration 2.0 × 10⁻⁴ M is measured in a 1.00 cm cuvette at a wavelength where ε = 1.20 × 10³ L mol⁻¹ cm⁻¹. Find the absorbance and the percent transmittance.
A = εlc = (1.20 × 10³)(1.00)(2.0 × 10⁻⁴) = 0.240.
T = 10^(−A) = 10^(−0.240) = 0.575, so %T = 57.5%.
Example 2: unknown from a calibration curve
Standards of a substance give A = 0.30 at 0.050 M and A = 0.60 at 0.100 M, measured at l = 1.00 cm. An unknown of the same substance gives A = 0.45. Find its concentration and the value of ε.
Slope = 0.60 / 0.100 = 6.0 L/mol. Concentration = A / slope = 0.45 / 6.0 = 0.075 M.
Since slope = εl and l = 1.00 cm, ε = 6.0 L mol⁻¹ cm⁻¹.
Traps Specific to This Topic
Transmittance does not halve when concentration doubles. A solution with A = 0.70 has T = 0.20; doubling its concentration gives A = 1.40 and T = 0.040. Absorbance doubled, but transmittance fell to one fifth, not one half. Any answer that scales T linearly is wrong.
If two solutions of the same substance show equal absorbance in different cuvettes, their concentrations are not equal. The solution in the shorter cuvette must be more concentrated to make up for the shorter path.
At high concentrations the calibration curve bends and Beer’s law fails, because absorbing particles are crowded close enough to interact with each other and with neighbours’ charges, changing how each one absorbs. Dilute the sample into the linear range instead of extrapolating the line.
Combining changes multiplies through A = εlc. Doubling concentration while halving path length leaves absorbance unchanged, because the two factors cancel. Work each factor separately rather than guessing the combined effect.