Trial
$\left[ Cu ^{2+}\right]$Absorbance

1
0.0250.124

2
0.0500.268

3
0.1000.520

4
0.1500.680






Using a spectrophotometer, a student measures the absorbance of four solutions of $CuSO_4$ at a given wavelength. The collected data is given in the table above. Which of the following is the most likely explanation for the discrepant data in trial 4?


AThe solution was at a lower temperature than the solutions in the other trials.
BThe measurement was made using a different spectrophotometer that uses a cell with a longer path length.
CThe solution was saturated and the flow of light through the solution was restricted.
DThe concentration of the solution was actually lower than $0.150 M$.

Verified Answer :

  • The Beer-Lambert law dictates a linear relationship between absorbance and concentration, \(A = \epsilon lc\).
  • Examining the ratio \(A/c\) reveals that the fourth trial significantly deviates from the linearity observed in the previous trials.
  • Among the options, a lower-than-expected concentration directly results in lower measured absorbance according to the law, making it the most probable experimental error.
  • The most likely explanation for the discrepant data in trial 4 is \(\boxed{D}\).

Explanation

  1. Problem Analysis and Linearity Check

The Beer-Lambert law relates the absorbance \(A\) of a solution to its concentration \(c\), path length \(l\), and molar absorptivity \(\epsilon\) by the equation \(A = \epsilon lc\). Under constant conditions (the same spectrophotometer and wavelength), \(\epsilon\) and \(l\) are constant, implying that absorbance \(A\) should be directly proportional to concentration \(c\). A plot of \(A\) versus \(c\) should yield a straight line passing through the origin. We can evaluate the data by calculating the ratio \(A/c\) for each trial:

  • Trial 1: \(\frac{0.124}{0.025} = 4.96\)
  • Trial 2: \(\frac{0.268}{0.050} = 5.36\)
  • Trial 3: \(\frac{0.520}{0.100} = 5.20\)
  • Trial 4: \(\frac{0.680}{0.150} \approx 4.53\)

The first three trials show a consistent range for the ratio, while the fourth trial shows a significantly lower absorbance than expected by the trend.

  1. Evaluating Potential Causes

To identify the most likely cause, we evaluate the options:

  • Option A: Lower temperature generally has a minimal effect on the absorbance of copper sulfate solutions in standard laboratory conditions, making it an unlikely cause for a significant discrepancy.
  • Option B: A longer path length (\(l\)) would increase the absorbance according to \(A = \epsilon lc\). Since the observed absorbance in trial 4 is lower, this is incorrect.
  • Option C: If the solution were saturated, the Beer-Lambert law might fail due to non-linearity; however, "restricted flow" is not a standard description of a common experimental error. Saturation would often result in instrument readings that are highly unpredictable or erratic rather than just slightly lower than expected.
  • Option D: If the concentration of the solution prepared for trial 4 was lower than 0.150 M, the absorbance would naturally be lower. This is a very common experimental error in laboratory settings, such as improper dilution or inaccurate measurement of the solute during preparation. Given the linear nature of the Beer-Lambert law, a lower concentration directly accounts for the lower measured absorbance.
  1. Conclusion

Comparing the options, option D is the most standard and scientifically sound explanation for the lower absorbance in trial 4. Experimental errors in preparing the solution concentration (resulting in a lower actual concentration) directly lead to a decrease in the measured absorbance, consistent with the linear relationship expected from the Beer-Lambert Law. Therefore, the most likely explanation is that the concentration of the solution was actually lower than 0.150 M.

Examples

In real-world laboratories, spectrophotometry is used to determine the concentration of substances in environmental water samples. If an analyst observes that an experimental data point deviates from the expected linear calibration curve, they must troubleshoot the cause. Recognizing that a lower-than-expected absorbance value often indicates an error in sample preparation (a lower-than-intended concentration) is a critical diagnostic skill for ensuring accurate chemical analysis and environmental monitoring.