Standard Addition

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The method of standard addition is used in instrumental analysis to determine concentration of a substance (analyte) in an unknown sample by comparison to a set of samples of known concentration, similar to using a calibration curve. Standard addition can be applied to most analytical techniques and is used instead of a calibration curve to solve the matrix effect problem.

The matrix effect problem occurs when the unknown sample contains many impurities. If impurities present in the unknown interact with the analyte to change the instrumental response or themselves produce an instrumental response, then a calibration curve based on pure analyte samples will give an incorrect determination.

One way to solve this problem is to use standard addition. The standard solution (solution of known concentration of analyte) is added to the unknown solution so any impurities in the unknown are accounted for in the calibration. The operator does not know how much was in the solution initially but he does know how much standard solution was added, and he knows how the readings changed before and after adding the standard solution so he can extrapolate and determine the concentration initially in the unknown solution. In practice, the volume of standard solution added is kept small to avoid dilution of the unknown impurities.

The graph above is an example of a standard addition plot used to determine the concentration of calcium in an unknown sample by atomic absorption spectroscopy. The point at zero concentration added Ca is the reading of the unknown, the other points are the readings after adding increasing amounts ('spikes') of standard solution. The absolute value of the x-intercept is the concentration of Ca in the unknown, in this case 1.69E-6 g/mL.

[edit] References

• Harris, Daniel C. (2003). Quantitative Chemical Analysis 6th Edition. New York: W.H. Freeman.