30/03/2022

Techniques non-destructive: techniques without destructing the sample (ex: X-ray diffraction)
Most that are carried out in solution are destructive

But there are some of them that are not destructive:

The don’t change the pure sample or the don’t get consume when we are carrying out the
measurement. Ex: glass membrane
Micro electrodes vs Macro electrodes.

Macro electrode

Micro electrode is ever so tiny that no matter how long it takes the measurement that is not
enough to destroy de sample (once it is the sample in solution it’s not consume) it’s a non-
destructive technique. Since they don’t consume the sample, they are commonly named as
color indicator electrodes. Glass membrane is an indicator electrode.

BULK ELECTROLYSIS PROCESSES: ELECTROGRAVIMETRY AND COULOMETRY

In this, all the bulk is transformed. We consume all the sample.

Solution containing Fe2+.We may carry out the reduction of it will follow the faraday form. In a
coulometric analysis we completely reduce all the copper, and we measure the current that
reduces and the time it takes to reduce all.
The cathode should be a macro electrode. In top of this area the reaction takes place.
Exponential decay of the current because the amount of copper is reduced is less and less and
we have a graph with a exponential curve. (We then have to make the integral.
We see that the asymptote comes to 0 but it takes very long. In the end this is the area.
(Approach)
Another approach is that we have a constant current. If the current is constant then the
amount that is reduce is constant also, so then we depend only on time (this makes the time
shorter and its much simple)
The main type of coulometry is the one at which current is constant.
In the coulometry we just measure the process carries out in the cathode, but we don’t care
where the product goes.

Something similar is electrogravimetry where we measure the amount of product deposited in

the cathode. Is just to apply the given current, we fix the potential and then at a given
potential the copper starts to deposit the hall of the sample in the cathode, and we calculate
by subtracting this amount to the weight of the cathode.

Both are techniques which consume all the original sample in solution. COMPLETELY. So, they
are not indicators because they destroy the original sample.

Macro vs Micro revisited:

Micro: tiny times, tiny currents

Macro: larger times, larger currents, the charge increases.

When we deposit a metal in a large area, at the potential we made be operation is negative,
the protons present in solution get reduce to H-(hydride )and transforms into hydrogen and
produces bubbles. Gas is emanating from the metal, and it destroys the electrodes.
An overpotential is the excess of potential we must reach to compense the difference of
potential for do the reverse of hydrogen.

We need to consider in a sample which is the omic drop. An extra negative potential to
overcome the resistance of the movement of the ions that flow to the current.

Another general idea is that when we use the coulometry analysis, when we use constant
current, classically is called the constant coulometric titration. When we use to generate in situ
species that are instable. We can produce iodine in situ. In a large anode. Fe+ we titrate it with
potassium iodine excess and the iodide is going to be oxidized into iodine and we generate in
situ de iodine. The reaction process very faster and all immediately reacts with the copper. We
measure the time, we know the current because is constant, we know the number of electrons
involved and then we can know the concentration of analyte. Using a large area electrode.

05/04/2022

LESSON 9: FUNDAMENTALS OF MOLECULAR ABSORTION SPECTROSCOPY

provides A LARGE PORCENTAGES OF TECHNIQUES IN A QUANTITATIVE POINT OF VIEW

Some spectroscopy techniques are good as well for qualitative analysis.

Type of experiment: Absorption, Emission, Fluorescence and Scattering
They have to do with the quantize levels of matter of a sample.
Electromagnetic radiation is a huge panorama.
There is only a tiny portion of those energy what we call the visible spectrum which our eye
can detect it. This is the visible spectrum, and the limits are not completely fix.
In round numbers the visible spectrum covers from 400 to 800.

Have to do with the interaction of matter with just the electric field of the electromagnetic
radiation. This field doe interact with radiation and the experience is that when such radiation
goes through the cubit what we see is a decrease of intensity that has to do with the
composition of the sample. This decrease proves that there is an interaction with the analyte.
The basis of these three interactions:

Absorption process: (very common)

if that energy resolute in a decrease in the power and if its’s due to an absorption radiation if
the transition from the ground to the excited state releases energy. The activation is by non-
radiational emits.

But, there can be no release of radiation in the process of coming back to the ground state
(does not emit any photon).

The emission process is not radiational but just providing heat. Once we are in the excited
state, the deactivation tis a radiational process in which a photon is emit. When we combine
both processes, we have fluorescence.
In all, all the energetic levels are quantized. That’s why the atoms absorb at just their energies.
That is the begging of the qualitative analysis, just emission techniques. In emission processes
we will see why the selectivity helps. There are many substances that absorb at the very
similar length waves, so it is difficult to distinguish.
This type of interaction is going to help us to develop a lot of analytical procedure with a very
big confidence.

Always we are going to talk about aquous solutions, this solution is put in a cell and we
measure the radiation. This type of techniques is destroying because we need to dissolve the
solution, but they are not destructive in the mean that we don’t destroy the sample with the
light that passes through.

How is it that the power (intensity) decreases coming through the sample (LAMBER BEER
LAW)
The absorption phenomena are related to those photons that are released in this process. My
analyte may absorb a very tiny portion of the spectrum. Some of energy is absorb and the rest
is going to go through with no problem. So, to monitor this we need specific wavelengths. It is
difficult to select pure wavelengths. You never have a pure line of the spectrum, we have
bands. Bands meaning the interval. The narrow the band, the better. Specially in absorption
we will talk about bands
The lost of intensity after the interaction with the analyte is this lamber bear law. It will
decrease by a certain function depending of the wavelength has passed through.
b is the symbol of the path wave( of the cubete).Unless we are told something else, this we
assume to be 1 cm.
8/04/2022

Titrations with photometric cells.

Analyte + titrant to give a given product

Titration plots now, they are linear shapes . We always must fix the wavelength at which we
measure the absorbance. At that given landa we should know the molar absorptivity of all
species involved at the same wavelength. And just by knowing these values we should know
how to trite this curve.

One common one is the complexometric.

First situation: Ea=0, Et=0, Eproduct mayor que 0.

The product does not absorb.

In case c, in which the only one that absorbs is the analyte, the absorbance will decreases as
well the analyte decreases. So in the cubete we will have the remains of titrant and product.

Thanks to this linear shape we can see very well the equivalence point that’s why we don’t
have to be careful because we will find it with very aquiricy. The importance of this type of
linear plots has also to do, is that in some instances we don’t have to put large aditions to
reach the stoichiometric point.If we just add a few aditions we don’t need to proced with
more,WE EXTRAPOLATE WITH THE X AXIS AND THEN WE HAVE IT !!!.We save money because
we consume very little of titrant.

residual absorbance, that is null if the

absorbance is 0.
In case d, the product is the only one that does not absorb. But also, this plot tells us that
molar absorptivity of the analyte is large than the titrant one. In the post equivalence, the
titrant does absorb and is reflected the difference with the analyte in the graph.

The comparation of e and f is that in f the product is a better absorbance than the titrant and
in e the absorbance of the titrant is better.

*CUANTO MEJOR ABSORBA MAS PRONUNCIADA ES LA PENDIENTE DE LA RECTA DIBUJADA EN

LA GRAFICA CON RESPECTO A LA OTRA PARTE DE LA REACCION.UN EJEMPLO, EN LA GRAFICA E
VEMOS QUE ES MAS PRONUNCIADA LA RECTA DE VALORANTE QUE DE LA DE PRODUCTO
PORQUE VEMOS QUE AMBOS ABSORBEN PERO EL VALORANTE TIENE MEJOR ABSORCION QUE
EL PRODUCTO.*

Let´s see an example:

At the same time that the copper is decreasing is being generated the complex that we can see
that does absorb. Copper EDTA complex is contributing so we have the contribution of them
And we can´t reach a null situation in this case. The excess of the ligand is the one that grows
after the equivalence point. No matter what type of combination we have we should be able
to predict the type of curve.
We might carry out the same quantitation with the same ligand in the same step, but we can’t
titrate both in the same step. EDTA is going to react with bismuth and only when all the
bismuth Is complexed the EDTA is going to start with copper. The molar absorptivity of the
EDTA itself should be null.
At the very beginning we have both and the titrant starts to complex but the bismuth complex
that not absorbed so the absorbance will remain up to 0. Once we reach the full complexation
of bismuth we complex the copper that does absorbed and the line increases. When the
copper does completely complex no matter how much EDTA we add, that is going to come null
the absorbance of EDTA.

In exercise 11 of the seminar, the tell us if the copper will be advisable to detect then end
point. The copper is divalent and iron is trivalent son the constant of iron will be larger than
the copper one. The complex of copper with EDTA does absorb so it will start to increase in
the graph.