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Spectrophotometric Titrations
• If at least one species in a complexation titration absorbs
electromagnetic radiation, we can identify the end point by monitoring
the titrand’s absorbance at a carefully selected wavelength.
• For example, we can identify the end point for a titration of Cu2+ with
EDTA, in the presence of NH3 by monitoring the titrand’s absorbance at a
wavelength of 745 nm, where the Cu(NH3)4
2+ complex absorbs strongly.
• At the beginning of the titration the absorbance is at a maximum. As we
add EDTA the concentration of Cu(NH3)4
2+, and thus the
absorbance, decreases as EDTA displaces NH3.
• After the equivalence point the absorbance remains essentially
unchanged
Acorr = A × (VEDTA + VCu)/VCu
where VEDTA and VCVCuu are, respectively, the volumes of EDTA
and Cu.
• Correcting the absorbance for the titrand’s dilution ensures
that the spectrophotometric titration curve consists of
linear segments that we can extrapolate to find the end
point. Other common spectrophotometric titration curves
are shown in panels b-f.
The resulting spectrophotometric titration is shown below in
panel (a). Note that the titration curve’s y-axis is not the actual
absorbance, A, but a corrected absorbance, Acorr
As we add EDTA the concentration of Cu(NH3)4
2+,
and thus the absorbance, decreases as EDTA
displaces NH3. After the equivalence point the
absorbance remains essentially unchanged
Spectrophotometric titrations

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Spectrophotometric titrations

  • 1. Spectrophotometric Titrations • If at least one species in a complexation titration absorbs electromagnetic radiation, we can identify the end point by monitoring the titrand’s absorbance at a carefully selected wavelength. • For example, we can identify the end point for a titration of Cu2+ with EDTA, in the presence of NH3 by monitoring the titrand’s absorbance at a wavelength of 745 nm, where the Cu(NH3)4 2+ complex absorbs strongly. • At the beginning of the titration the absorbance is at a maximum. As we add EDTA the concentration of Cu(NH3)4 2+, and thus the absorbance, decreases as EDTA displaces NH3. • After the equivalence point the absorbance remains essentially unchanged
  • 2. Acorr = A × (VEDTA + VCu)/VCu where VEDTA and VCVCuu are, respectively, the volumes of EDTA and Cu. • Correcting the absorbance for the titrand’s dilution ensures that the spectrophotometric titration curve consists of linear segments that we can extrapolate to find the end point. Other common spectrophotometric titration curves are shown in panels b-f. The resulting spectrophotometric titration is shown below in panel (a). Note that the titration curve’s y-axis is not the actual absorbance, A, but a corrected absorbance, Acorr
  • 3. As we add EDTA the concentration of Cu(NH3)4 2+, and thus the absorbance, decreases as EDTA displaces NH3. After the equivalence point the absorbance remains essentially unchanged