50.00 mL of 0.1000M V2+ is titrated with 0.

05000M
Sn4+. Calculate potentials after the addition of
10.00, 30.00, 50.00, 55.00, and 60.00 mL of the
titrant.
INTRODUCTION TO UV-Vis
SPECTROSCOPY
SPECTROSCOPY
• Spectroscopy is the study of the interaction between matter and
electromagnetic radiation.
• Spectroscopy originated through the study of visible light
dispersed according to its wavelength, by a prism.
Electromagnetic Spectrum

Important: As the wavelength gets shorter, the energy of the radiation increases.

Important: As the wavelength gets shorter, the energy of

the radiation increases.
Particle Nature of Radiation
• Electromagnetic radiation is also described as having the
properties of particles.
• Molecules exist in a certain number of possible states
corresponding to definite amounts of energy.
• Molecules can absorb energy and change to a higher energy
level called the excited state.
• The amount of energy absorbed in this transition is exactly
equal to the energy difference between the states.
UV-Vis Spectroscopy
• Visible (380-780 nm)
• Ultraviolet (UV) (10 – 380 nm).
• Below about 200 nm, air absorbs the UV light and instruments
must be operated under a vacuum
• UV/Vis spectra can be used to some extent for compound
identification, however, many compounds have similar spectra.
• Solvents can cause a shift in the absorbed wavelengths.
Therefore, the same solvent must be used when comparing
absorbance spectra for identification purposes.
• Many inorganic species also absorb energy in the UV/Vis region
of the spectrum.
Absorption Process and Beer’s Law
• Incident radiation P0 can be absorbed by the analyte resulting in
a transmitted radiation P.
• This process transfers energy to the molecule and results in a
decrease in the intensity of the incident electromagnetic
radiation.

• Transmittance: %T = P/ P0 x 100
• Absorbance: A= -log T
Absorption Process and Beer’s Law
• According to Beer’s law, absorbance is directly proportional to
the concentration of the absorbing species, c, and to the path
length, b, of the absorbing medium.
A = abc
• a is a proportionality constant called the absorptivity (L g-1 cm-1)
• When we express the concentration in the equation in moles
per liter and b in cm, the proportionality constant is called the
molar absorptivity and is given the symbol ε. Thus,
A = εbc (ε is in L mol-1 cm-1)
A 5.00 × 10–4 M solution of an analyte is placed in a sample cell with a
pathlength of 1.00 cm. When measured at a wavelength of 490 nm, the
solution’s absorbance is 0.338. What is the analyte’s molar absorptivity at this
wavelength?
Quantitative Analysis
• Calibration Method: standards should approximate as close as
possible the overall composition of the actual samples, and
should encompass a reasonable range of the analyte
concentration

• Standard-Addition Method: involves adding one or more

increments of a standard solution to sample aliquots of the
same size; helpful in counteracting matrix effects
Analysis of Mixtures
• The total absorbance of a solution at any given wavelength is
equal to the sum of the absorbances of the individual
components in the solution

• A1 = εM1bcM + εN1bcN
• A2 = εM2bcM + εN2bcN
• Calculate the concentrations of A and B in the unknown solution
from the data obtained from the absorption spectra of two
colored substances A and B using 1.00-cm cell.

Solution Molarity A450nm A750nm

A alone 5.00 x 10-4 0.800 0.100
B alone 2.00 x 10-4 0.100 0.600
A+B unknown 0.600 1.000