SPECTROPHOTOMETRIC Experiment 5

DETERMINATION OF Keq OF FeSCN 2+

ABSORPTION SPECTROSCOPY
Attenuation of certain frequencies of electromagnetic
radiation by a chemical species
Energy of photon = Energy difference between ground state
and higher energy state of absorbing species
ABSORPTION SPECTROSCOPY

𝐼 𝑃
𝑇= =
𝐼𝑜 𝑃𝑜
T = transmittance
I = transmitted light
Io = Incident light
P = power of transmitted light
Po = power of incident light
ABSORBANCE
BEER’S LAW

ε = molar absorptivity (L/ mol-cm)

b = path length
c = concentration of absorbing species (M)
 DOUBLE-BEAM UV-VIS SPECTROPHOTOMETER

Source of radiant energy

- Deuterium of hydrogen lamp for UV
- Tungsten lamp for visible
 DOUBLE-BEAM UV-VIS SPECTROPHOTOMETER

Wavelength selector
- Isolates wavelength
- Monochromator = grating or prism to disperse a radiation to component wavelengths
 DOUBLE-BEAM UV-VIS SPECTROPHOTOMETER

Sample containers
- Transparent to radiation
- Plastic or ordinary glass for visible region
- Quartz (silica glass) for both UV and visible
 DOUBLE-BEAM UV-VIS SPECTROPHOTOMETER

Radiation detector/transducer
- Converts radiant energy to a measurable signal
- Detector: Phototransducer
 DOUBLE-BEAM UV-VIS SPECTROPHOTOMETER

A signal processor and readout device

EXPERIMENT PROPER
Fe3+(aq) + SCN- (aq) + 5H2O(l) ⇌ [Fe(SCN)(H2O)5]2+ (aq)

FeCl3 KSCN Blood-red complex

Pentaaquathiocyanatoiron (III)

Chromophore: Fe(III) - SCN

EXPERIMENT PROPER
Calibration curve
Solution 0.002 M FeCl3, mL 0.20 M KSCN, mL 0.10 M HCl, mL
Blank 0.00 1.00 9.00
Standard 1 0.10 1.00 8.90
Standard 2 0.25 1.00 8.75
Standard 3 0.50 1.00 8.50
Standard 4 1.00 1.00 8.00
Standard 5 2.00 1.00 7.00
EXPERIMENT PROPER
Calibration curve
Solution [FeCl3] [KSCN] [FeSCN2+]
Blank 0.00 0.02 0.00
Standard 1 2.0 x 10-5 0.02 2.0 x 10-5
Standard 2 5.0 x 10-5 0.02 5.0 x 10-5
Standard 3 1.0 x 10-4 0.02 1.0 x 10-4
Standard 4 2.0 x 10-4 0.02 2.0 x 10-4
Standard 5 4.0 x 10-4 0.02 4.0 x 10-4

𝝀𝐦𝐚𝐱 = 𝟒𝟔𝟖. 𝟓 𝐧𝐦
CALIBRATION CURVE

ε = molar absorptivity (L/ mol-cm) Exptl error

y=m x+b

Absorbance concentration of absorbing species (M)

CALIBRATION CURVE
0.6
0.5
0.4
0.3
Abs 0.2
0.1
0
0 2 4 6
[FeSCN2+], M
Figure 1. Absorbance against concentration of FeSCN2+.

Theoretical ε of FeSCN2+: 3550 M-1cm-1

Source: http://www.lahc.edu/classes/chemistry/arias/Lab4Equilibriasp11.pdf
UNKNOWN SOLUTIONS
Abs = 3550 [FeSCN2+]eq
[Fe(SCN)2+] eq = interpolate from the calibration curve
[Fe3+] eq = [Fe3+] in - [Fe(SCN)2+] eq
[SCN-]eq = [SCN-]in - [Fe(SCN)2+] eq
SIGNIFICANCE OF THE HCl IN THE SOLUTION PREPARATION

 HCl suppresses the formation of hydroxo-complexes

of Fe(III). These complexes are brown in color and may
cause interference during the UV-Vis analysis.
[Fe(H2O)6]3+ ⇌ [Fe(H2O)5(OH)]2+ + H+

 Also, formation of hydroxide precipitates may occur.

The concentration of FeSCN 2+ in the standard solution is equal to the
concentration of SCN -, the limiting reactant. Is this condition always true?
If not, what is(are) the condition(s) for this to be true?

Fe3+(aq) + SCN- (aq) + 5H2O(l) ⇌ [Fe(SCN)(H2O)5]2+

This condition will only be true if and only if SCN- is added in

great excess. This would shift the equilibrium to the right and
exhausting the limiting reactant. When this happens,
[FeSCN2+]eq is approximately equal to [Fe3+]in.
Solutions containing Fe3+ are colored thus absorb at the visible
region. Explain why the absorbance readings in the experiment
correspond only to the absorption of the complex, FeSCN 2+.

A blank reading is performed to subtract from all

absorbance readings not due to the analyte.
Thus, the absorbance reading of the samples is
only due to the [Fe(SCN)]2+(eq) in the solution.
Can distilled water which has zero absorbance
3+
be used as blank instead of the Fe solution?
No because the absorbance of excess Fe3+ in
the analyte solutions should be cancelled out.
This would not be possible if only water is used.
Account for the difference between the literature value and the
experimentally determined value of the equilibrium constant.
 Temperature
 Beer’s law has its limitations as light is not perfectly
monochromatic, at high concentrations it becomes non-
linear. If high concentration solutions were used, it
would mean that the Beer’s law equation is not
applicable for the analysis.
 Instrumental limitations: possible entry of stray light,
reflection at cuvette surface.
 Account for the difference between the literature value and the
experimentally determined value of the equilibrium constant.

 Errors:
systematic - determinate errors: instrumental, methodic, personal
random errors – indeterminate
gross errors
Why should we measure absorbance at the
analytical wavelength?
At this wavelength, the absorbance is most
sensitive when concentration is varied.