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Copper was determined in a river water sample by atomic absorption spectrometry and the method of standard additions. For the addition, \(100.0 \mu \mathrm{L}\) of a \(1000.0-\mu \mathrm{g} / \mathrm{mL}\) Cu standard was added to \(100.0 \mathrm{~mL}\) of solution. The following data were obtained: Absorbance of reagent blank \(=0.020\) Absorbance of sample \(=0.520\) Absorbance of sample plus addition \(-\) blank \(=1.020\) (a) Calculate the copper concentration in the sample. (b) Later studies showed that the reagent blank used to obtain the above data was inadequate and that the actual blank absorbance was \(0.100\). Find the copper concentration with the appropriate blank, and determine the error caused by using an improper blank.

Short Answer

Expert verified
(a) 1.08 \(\mu\)g/mL; (b) Corrected: 0.77 \(\mu\)g/mL, error: 0.31 \(\mu\)g/mL.

Step by step solution

01

Identify Key Data and Concept

In this problem, we use the method of standard additions in atomic absorption spectrometry to calculate copper concentration in a river water sample. Data includes the reagent blank, absorbance of the sample, and absorbance after standard addition.
02

Calculate Concentration of Added Copper

To determine the concentration of the added copper standard, first compute the moles of copper added: 0.1 mL \(\times\) 1000 \(\mu\)g/mL = 100 \(\mu\)g. Convert to \(\mu\)g/mL in a 100 mL sample: 100 \(\mu\)g \(/\) 100 mL = 1 \(\mu\)g/mL.
03

Find Copper Concentration using Initial Blank

Using the method of standard additions and the provided absorbances:For the sample, absorbance = 0.520. Total signal of sample + standard = 1.020 (after subtracting blank). Using the proportionality for concentration and absorbance, set up: \(C + 1 = \frac{1.020}{0.520}C\)Solve for \(C\): \(C = \frac{1.020\times 0.520}{1.020 - 0.520} = 1.08 \mu\)g/mL.
04

Recalculate with Accurate Blank

With the accurate blank absorbance, correct the observed values:New sample absorbance = 0.520 - 0.100 = 0.420. New combination absorbance = 1.020 - 0.100 = 0.920.Set up the relation: \(C + 1 = \frac{0.920}{0.420}C\) Solving, \(C = \frac{0.920 \times 0.420}{0.920 - 0.420} = 0.77 \mu\)g/mL.
05

Calculate Error Due to Incorrect Blank

The initial copper concentration was found to be 1.08 \(\mu\)g/mL with the wrong blank, while the correct concentration is 0.77 \(\mu\)g/mL. Thus, the error is 1.08 - 0.77 = 0.31 \(\mu\)g/mL.

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Key Concepts

These are the key concepts you need to understand to accurately answer the question.

Copper Determination
When determining the concentration of copper in a sample, one effective method is through atomic absorption spectrometry. This technique relies on measuring the absorbance of light by copper atoms in the sample. The more copper present, the more light is absorbed. As light of a specific wavelength shines through a sample, copper atoms absorb this light, and an instrument records the decrease in light intensity. This is the absorbance value, which is directly proportional to copper concentration according to Beer's Law. Beer's Law states that absorbance ( A ) is equal to the molar absorptivity ( ε ) times the path length ( l ) and the concentration ( c ): A = εlc . By comparing the absorbance of the unknown sample to a known standard, we can calculate the copper concentration in the sample.
Method of Standard Additions
The method of standard additions is a powerful technique in analytical chemistry, especially useful when sample matrix effects are concerning. In this method, a known quantity of the analyte (in our case, copper) is added to the sample, and the change in absorbance is measured.
  • Initially, measure the absorbance of the sample without any added standard.
  • Add a known concentration of the analyte to the sample and measure the absorbance again.
The beauty of this method is that it compensates for matrix effects that may alter absorbance readings. The change in absorbance relates directly to the amount of analyte added, which can be used to back-calculate the concentration in the original sample. This is accomplished using the following equation:\[C_{sample} = C_{added} \times \frac{A_{sample}}{A_{increase}}\]Where C_{sample} is the concentration of copper in the sample, C_{added} is the concentration of the added standard, A_{sample} is the absorbance of the original sample, and A_{increase} is the increase in absorbance due to the standard addition.
Reagent Blank Correction
Correcting for the reagent blank is crucial in ensuring accurate analytical measurements. A reagent blank contains all the components of the test sample except the analyte of interest; in this case, it lacks copper. The absorbance reading of the reagent blank provides a baseline to account for any background absorbance caused by the sample matrix or reagents themselves. By subtracting the blank absorbance from the sample absorbance, we eliminate these background effects, isolating the signal due to copper alone. It's critical, as demonstrated, to use an accurate blank absorbance. Incorrect blank values lead to errors in calculated concentrations, which were apparent in the exercise when the wrong blank value initially led to an overestimation of the copper concentration.
Analytical Chemistry Problem Solving
Analytical chemistry often involves complex problem-solving skills to tackle measurement uncertainties and resolve deviations. For instance, in the given exercise, identifying inaccurate blank readings and correcting them demonstrates a critical problem-solving approach. To address analytical problems effectively, consider these steps:
  • Identify potential sources of error, such as improper blank measurements or equipment calibration issues.
  • Correct these errors by re-evaluating absorbance readings with more reliable blank data or improving calibration processes.
  • Recalculate concentrations rigorously and compare them with initial findings to gauge the accuracy.
Thorough problem-solving not only enhances data reliability but also ensures precise analytical outcomes, fostering a deeper understanding of the studied phenomena.

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