A18 Appendixes

AP P E N D I X 3 Spectral Analysis
Although volumetric and gravimetric analyses are still very commonly used, spectros-
copy is the technique most often used for modern chemical analysis. Spectroscopy is
the study of electromagnetic radiation emitted or absorbed by a given chemical spe-
cies. Since the quantity of radiation absorbed or emitted can be related to the quantity
of the absorbing or emitting species present, this technique can be used for quantitative
analysis. There are many spectroscopic techniques, as electromagnetic radiation spans
a wide range of energies to include X rays; ultraviolet, infrared, and visible light; and
microwaves, to name a few of its familiar forms. We will consider here only one pro-
cedure, which is based on the absorption of visible light.
If a liquid is colored, it is because some component of the liquid absorbs visible
light. In a solution the greater the concentration of the light-absorbing substance, the
more light absorbed, and the more intense the color of the solution.
The quantity of light absorbed by a substance can be measured by a spectrophotom-
eter, shown schematically in Fig. A.6. This instrument consists of a source that emits
all wavelengths of light in the visible region (wavelengths of ,400 to 700 nm); a
monochromator, which selects a given wavelength of light; a sample holder for the
solution being measured; and a detector, which compares the intensity of incident light
I0 to the intensity of light after it has passed through the sample I. The ratio IyI0, called
the transmittance, is a measure of the fraction of light that passes through the sample.
The amount of light absorbed is given by the absorbance A, where
I
A 5 2log
I0
The absorbance can be expressed by the Beer–Lambert law:
A 5 Plc
where P is the molar absorptivity or the molar extinction coefficient (in L/mol ? cm),
l is the distance the light travels through the solution (in cm), and c is the concentration
of the absorbing species (in mol/L). The Beer–Lambert law is the basis for using spec-
troscopy in quantitative analysis. If P and l are known, measuring A for a solution al-
lows us to calculate the concentration of the absorbing species in the solution.
Suppose we have a pink solution containing an unknown concentration of Co2(aq)
ions. A sample of this solution is placed in a spectrophotometer, and the absorbance is
measured at a wavelength where P for Co21(aq) is known to be 12 L/mol ? cm. The
absorbance A is found to be 0.60. The width of the sample tube is 1.0 cm. We want to
determine the concentration of Co21(aq) in the solution. This problem can be solved
by a straightforward application of the Beer–Lambert law,
A 5 Plc

I0 I

Source Monochromator Sample Detector

FIGURE A.6 A schematic diagram of a simple spectrophotometer. The source emits all wave-
lengths of visible light, which are dispersed using a prism or grating and then focused, one
wavelength at a time, onto the sample. The detector compares the intensity of the incident light (I0)
to the intensity of the light after it has passed through the sample (l).

Copyright 2018 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. WCN 02-200-203
 Appendixes A19

where
A 5 0.60
12 L
P5
mol # cm
l 5 light path 5 1.0 cm
Solving for the concentration gives

A 0.06
c5 5 5 5.0 3 1022 mol/L
a12 b 11.0 cm2
Pl L
mol # cm

To obtain the unknown concentration of an absorbing species from the measured

absorbance, we must know the product Pl, since
A
c5
Pl
We can obtain the product Pl by measuring the absorbance of a solution of known
concentration, since
Measured using a
o spectrophotometer
A
Pl 5
c
r Known from making up
the solution

However, a more accurate value of the product Pl can be obtained by plotting A versus
c for a series of solutions. Note that the equation A 5 Plc gives a straight line with
slope Pl when A is plotted against c.
For example, consider the following typical spectroscopic analysis. A sample of
steel from a bicycle frame is to be analyzed to determine its manganese content. The
procedure involves weighing out a sample of the steel, dissolving it in strong acid,
treating the resulting solution with a very strong oxidizing agent to convert all the
manganese to permanganate ion (MnO42), and then using spectroscopy to determine
the concentration of the intensely purple MnO42 ions in the solution. To do this, how-
ever, the value of Pl for MnO42 must be determined at an appropriate wavelength. The
absorbance values for four solutions with known MnO42 concentrations were mea-
sured to give the following data:

Concentration of
Solution MnO42 (mol/L) Absorbance
1 7.00 3 1025 0.175
24
2 1.00 3 10 0.250
24
3 2.00 3 10 0.500
4 3.50 3 1024 0.875

A plot of absorbance versus concentration for the solutions of known concentration is

shown in Fig. A.7. The slope of this line (change in Aychange in c) is 2.48 3 103 L/mol.
This quantity represents the product Pl.
A sample of the steel weighing 0.1523 g was dissolved and the unknown amount
of manganese was converted to MnO42 ions. Water was then added to give a solution
with a final volume of 100.0 mL. A portion of this solution was placed in a spectro-
photometer, and its absorbance was found to be 0.780. Using these data, we want to
calculate the percent manganese in the steel. The MnO42 ions from the manganese in

Copyright 2018 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. WCN 02-200-203
A20 Appendixes

1.00

0.90
0.780
0.80

0.70 0.558
Slope =
0.60 2.25 × 10 – 4

Absorbance
= 2.48 × 103 Δ A = 0.558
0.50

0.40

0.30

0.20 ΔC = 2.25 × 10 – 4
3.15 × 10 – 4
0.10

FIGURE A.7 A plot of absorbance 0

versus concentration of MnO42 in a series 1.0 × 10 – 4 2.0 × 10 – 4 3.0 × 10 – 4
of solutions of known concentration. Concentration (mol/L)

the dissolved steel sample show an absorbance of 0.780. Using the Beer–Lambert law,
we calculate the concentration of MnO42 in this solution:
A 0.780
c5 5 3 3.15 3 1024 mol/L
Pl 2.48 3 103 L/mol
There is a more direct way for finding c. Using a graph such as that in Fig. A.7
(often called a Beer’s law plot), we can read the concentration that corresponds to
A 5 0.780. This interpolation is shown by dashed lines on the graph. By this method,
c 5 3.15 3 1024 mol/L, which agrees with the value obtained above.
Recall that the original 0.1523-g steel sample was dissolved, the manganese was
converted to permanganate, and the volume was adjusted to 100.0 mL. We now know
that [MnO4] in that solution is 3.15 3 1024 M. Using this concentration, we can calcu-
late the total number of moles of MnO42 in that solution:
1L mol
molM nO42 5 100.0 mL 3 3 3.15 3 1024
1000 mL L
5 3.15 3 1025 mol
Since each mole of manganese in the original steel sample yields a mole of MnO4,
that is,
Oxidation
1 mol Mn 88888888n 1 mol MnO42
the original steel sample must have contained 3.15 3 1025 mole of manganese. The
mass of manganese present in the sample is
54.938 g of Mn
3.15 3 1025 mol Mn 3 5 1.73 3 1023 g of Mn
1 mol Mn
Since the steel sample weighed 0.1523 g, the present manganese in the steel is
1.73 3 1023 g of Mn
3 100 5 1.14%
1.523 3 1021 g of sample
This example illustrates a typical use of spectroscopy in quantitative analysis. The
steps commonly involved are as follows:
1. Preparation of a calibration plot (a Beer’s law plot) by measuring the absorbance
values of a series of solutions with known concentrations
2. Measurement of the absorbance of the solution of unknown concentration
3. Use of the calibration plot to determine the unknown concentration

Copyright 2018 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. WCN 02-200-203