Coulometry (Chapter 22-D)

Coulometry uses a direct relationship between the quantity of electrical

charge (Q) applied and the mole amount of substance (N) which is
exhaustively reduced at the cathode or oxidized at the anode.
Q = NnF
In other words, coulometric methods of analysis are based on measuring
the number of electrons that participate in a chemical redox reaction:
the total number of electrons used to complete the reaction is proportional
to the amount of analyte.

There are two types of coulometry that differ in the procedure for finding
charge, Q, needed to complete the redox reaction:
-- Constant-current coulometry (or coulometric titration)
Charge required to complete the reaction: Q = It,
where t is the time needed to reach the end-point of titration.
-- Controlled-potential coulometry
Example of coulometric analysis:
H2S in water may be analyzed by titration with iodine, I2, which is generated
electrolytically from iodide:
H2S(aq) + I2 → S(s) + 2H+(aq) + 2I-(aq).
To 50.0 mL-sample of water, excess KI was added. To complete the titration,
electrolysis required passing a constant current of 52.6 mA for 13.53 min.
Calculate the concentration of H2S (in ppm) in the sample.
Solution:
Generation of iodine via electrolysis: 2I- → I2 + 2e-
Moles of I2 generated:
It
N= = 2.2110-4 mol
nF
Moles H2S titrated = moles I2 generated = 2.2110-4 mol.
Therefore, the concentration of H2S in the sample is:
(2.21x10-4 mol)(34.09 g/mol)
CH2S = = 1.50610-4 g/mL = 150.6 mg/mL =
50.0 mL = 150.6 ppm
 Introduction to Spectrophotometry (Chapter 22)
Properties of Light Light has a wave nature:

Wavelength, l – the distance between two nearest maxima of the wave.

Frequency, n – the number of complete oscillations per second.
n = c/l
where c is the speed of light: c  3.0×108 m/s in vacuo.
~
1/l = n - wavenumber (units cm-1).
 On the other hand, light has a particle nature:
a particle of light is called a photon.
~
Energy of a photon of light: E = hn = hc/l = hcn Einstein’s formula
where h is Plank’s constant, h = 6.63×10-34 J·s;
n – frequency;
l – wavelength;
c – speed of light.

By absorbing a photon, a molecule

increases its energy (is promoted from
Excited state the ground to excited state).

E = hn
By emitting a photon, excited molecule
returns to a lower-energy state
Ground state
(the lowest energy state)
 E = hn = hc/l
The higher the energy, the lower
the wavelength of light
 Absorption of Light
White light contains all of the wavelengths of visible spectrum (l 380-780 nm).
When white light passes through a substance, the substance absorbs definite
wavelengths; the rest of the wavelengths are transmitted through the substance.
Due to this, the transmitted light is not white:
we observe the color (as the wavelengths) complement of the absorbed color.

Colors of visible light:

Absorption maximum (l, nm) Color absorbed Color observed
380-420 Violet Green-yellow
420-440 Violet-blue Yellow
440-470 Blue Orange
470-500 Blue-green Red
500-520 Green Purple
520-550 Green-yellow Violet
550-580 Yellow Violet-blue
580-620 Orange Blue
620-680 Red Blue-green
680-780 Purple Green
A part of the molecule responsible for light absorption (and, therefore, for color)
is called a chromophore.

Absorption spectra

P0 – radiant power of the incident light;

P – radiant power of the exiting light

Absorption spectrum is
T = P/P0 - transmittance a plot of absorbance, A
vs. the wavelength, l
A = log P0/P = - log T - absorbance
 Dependence of absorbance on the concentration: Beer’s Law

Note:
Beer’s law works
in dilute solutions
only (C < 0.1 M).

Beer’s Law: A = ebC where A is absorbance;

C – concentration of the absorbing compound;
Absorbance is proportional e – molar absorptivity (or molar extinction
to the concentration coefficient);
b – light pathlength = cuvette thickness
Problem 1:
The transmittance, T, of a 0.0100 M solution of a colored substance in a
0.100-cm cuvette is 8.23%. Find the absorbance, A, of this solution and the
molar absorptivity, e.

Solution:
A = - log T = - log (0.0823) = 1.0846

By Beer’s law, A = ebC;

hence, e = A/bC = (1.0846)/(0.100 cm × 0.0100 M) = 1.08×103 M-1 cm-1
Beer’s Law in chemical analyses
Please review calibration
methods

Sample Beer’s law plot

(a calibration plot in
spectrophotometry)
A typical procedure for constructing a Beer’s Law calibration plot:
Step 1: Prepare a series of solutions of the colored analyte with known
concentrations (standard solutions) and a blank solution (containing no
analyte).
Step 2: Measure absorbance of the blank solution and the analyte
standard solutions. Correct the readings for the samples by subtracting the
reading for the blank.
Step 3: Using the least-squares method, make a linear plot of the blank-
corrected absorbance versus concentration of the analyte in the standard
solutions.
Important Reminder:
If absorbance of the standards was properly corrected for the absorbance
of the blank, you will obtain a linear calibration plot passing through the
origin point (intercept = 0); the linear equation is
A = (e b)·C = (slope)·C.
Then, concentration of the analyte in an unknown solution is found as
C = A /(slope).

However, if the blank-correction of the absorbance of the standards was

insufficient, the calibration plot intercept ≠ 0; the linear equation is
A = (e b)·C + intercept = (slope)·C + intercept.
Hence, the concentration of the analyte in an unknown solution is found as
C = (A – intercept)/(slope).
Problem:
A sample of a substance (FW=292.16 g/mol) was placed in a 5-mL volumetric
flask, dissolved in a small amount of water, and the volume was adjusted with
water to a 5.00-mL mark.
A 1.00-mL aliquote of the solution was placed in a 10-mL volumetric flask and
diluted with water to the mark. Absorption spectrum of this solution measured
in a 1.00-cm cuvet showed at 450 nm absorbance A = 0.427 (e = 6130 M-1cm-1).
(a) What was the concentration of the compound in the cuvet?
(b) What was the concentration of the compound in the 5-mL flask?
(c) How many milligrams of the compound was used to prepare the initial
solution?
Solution:
(a) Concentration of the compound in the cuvet:
C = A/(eb) = 0.427/((6130 M-1cm-1)(1.00 cm)) = 6.97×10-5 M
(b) Concentration of the compound in the 5-mL flask:
C = (6.97×10-5 M) × (10.00 mL)/(1.00 mL) = 6.97×10-4 M
Note: NEVER omit the dilution factor!!!

(c) Mass of the compound used to prepare the solution (in the 5-mL flask):
Mass = (6.97×10-4 M)(5.00×10-3 L) (292.16 g/mol) = 1.02×10-3 g = 1.02 mg
UV-Vis spectrophotometer is the instrument used for measuring the absorbance

Single-beam scheme

monochromator
What happens when a molecule absorbs a photon of UV-VIS light?
The molecule is promoted from the lowest-energy ground state to a
higher-energy excited state.
• In the excited state, a pair of electrons residing in the molecular
orbital may have either anti-parallel spins (spin quantum numbers
+1/2 and -1/2; this is so-called singlet state, S) or parallel spins
(+1/2 and +1/2 or -1/2 and -1/2; so-called triplet state, T).

• Electron transitions from the ground state S0 to higher-energy

orbitals, depending on the spin quantum number in the excited
state, may be S0→S1 or S0→T1.
Simultaneouisly with electron transitions, vibrational and rotational
transitions occur as well.
 What happens to absorbed energy?
Excited molecules can emit light. This process is called luminescence.
The two forms of luminescence:
-- Fluorescence - photon emission via electron transitions between states
with same spin quantum numbers, S1→S0
-- Phosphorescence - photon emission via electron transitions between
states with different spin quantum numbers, T1→S0

A principal difference between fluorescence and phosphorescence is in

the time scale: fluorescence is prompt, while phosphorescence is delayed.

Alternatively, excited molecules can relax without emitting radiation, via

collisions with other (not excited) molecules, for example, molecules of
solvent.
-- Radiationless relaxations happens via vibrational and rotational
electron transitions.
 Fluorescence Spectra

Energy absorbed by a colored substance

during its irradiation with light is emitted
back as fluorescence.
Fluorescence emission
spectrum is a plot of emission
intensity vs. the wavelength, l
 The ability of a substance to emit light as fluorescence is
characterized by its quantum efficiency (or quantum yield), Qf :
Qf = (Photons emitted)/(Photons absorbed)

Not all of the compounds are equally capable of producing

fluorescence.
The ability of a molecule to emit light depends on its structure.

A general trend observed: rigid molecules with delocalized systems

of electrons usually are strongly fluorescent;
while flexible molecules containing no (or only few) multiple bonds
show very weak fluorescence (or no fluorescence at all).
 H
OH C CH2
HC N
MeO
For example,
Quinine
N
 Fluorometer is the instrument used for measuring the fluorescence

-- Emission spectrum is obtained by irradiating (exciting) the substance at

a particular constant wavelength (lex) and measuring the emission intensity
at varied wavelength (lem).
-- The substance is usually excited at the wavelength at which it absorbs
light: lex is chosen as lmax in the absorption spectrum.
Absorption and emission spectra have mirror-image relationship.
Emission bands
have longer
wavelength and
lower energy than
their originating
absorption bands.

The shift of the

emission band
relative to the
corresponding
absorption band is
called the Stokes
shift.
-- Excitation spectrum is nearly same as the absorption spectrum of a
substance. Excitation and emission spectra have mirror-image
relationship.
-- Excitation spectrum is obtained by irradiating the substance at varied
wavelength (lex) and measuring the emission intensity at a particular constant
wavelength (lem).
 Molecular fluorescence spectroscopy is a VERY sensitive method.
Fluorescence intensity in dilute solutions is proportional to the
concentration of substance, similarly to the Beer’s Law:
Emission intensity, I = k P0 C
where k is a constant related to the molar absorptivity of the analyte, e,
and also to its quantum yield, Qf;
P0 is the energy of incident radiation;
C is the analyte concentration.

Sample calibration plot