Figures of Merit

1E Performance Characteristics of Instruments

Table 1-3 Numerical Criteria for Selecting Analytical Table 1-5 Figures of Merit for Precision of
Methods Analytical Methods
 Sensitivity

• Sensitivity (instrument or a method) measures its ability to

discriminate between small differences in analyte concentration.
• The quantitative definition of sensitivity that is accepted by
IUPAC is calibration sensitivity
• Calibration Sensitivity is the slope of the calibration curve at the
concentration of interest
• Most calibration curves are linear and may be represented by:
S = mc + Sblank (1-10)
where:
S : is the measured signal,
c : is the concentration of the analyte,
Sblank : is the instrumental signal for a blank,
m : is the slope of the straight line.
The quantity Sbl is the y-intercept of the straight line
 Sensitivity

• Mandel and Stiehler ➔ include precision in a meaningful

mathematical statement of sensitivity and proposed the following
definition for analytical sensitivity γ
γ = m / sS (1-11)

where:
m : is the slope of the calibration curve
sS : is the standard deviation of the measurement
 Detection Limit

Detection Limit is the minimum concentration or mass of analyte that can

be detected.
Sm = Sblank + 3s (1-12)

where:
Sm : is the minimum detectable signal for the analyte,
Sblank : is the instrumental signal for a blank,
s : is the standard deviation of the blank.

The detection limit is then given by:

S = mc + Sblank (1-10) (1-13)

A least-squares analysis of calibration data for the determination of lead based on its flame emission spectrum yielded the
equation
S = 1.12cPb + 0.312
where
cPb : is the lead concentration in ppm
S = mc + Sbl (1-10)
S : is a measure of the relative intensity of the lead emission line.
γ = m / sS (1-11)
The following replicate data were then obtained: Sm = Sblank + 3s

Conc., ppm Pb No. of Replications Mean Value of S Absolute standard deviation, s

10 10 11.62 0.15
1.00 10 1.12 0.025
0.000 24 0.0296 0.0082

Calculate:
(a) the calibration sensitivity.
(b) the analytical sensitivity at 1 and 10 ppm of Pb.
(c) the detection limit.
Every analytical measurement is made up of two
components:

signal and noise

Signal: carries information about the analyte

Noise: made up of extraneous information that is unwanted

because it degrades the accuracy and precision of an analysis
and also places a lower limit on the amount of analyte that can
be detected.
Signal-to-noise ratio
 Actual recording Average

Figure 5-1 Effect of noise on a current measurement:

(a) experimental strip-chart recording of a 0.910-15 A
direct current, (b) mean of the fluctuations. (Adapted
from T. Coor, J. Chem. Educ., 1968,45,A594. With
permission.)