X-RAY PHOTOELECTRON SPECTROSCOPY (X PS)

Chapter 3 of the book: Techniques for analysis and characterization of materials

Present by:

Kevin Fabia Abril Romero

Present to:

Pedro Nel Martinez Henao (Engineer)

Militar University of New Granada faculty of engineering

Engineering the materials

Cajicá 2022

IND C
CHEMICAL ANALYSIS: ATOMIC ABSORPTION AND EMISSIVITY

ABSORPTION AND ATOMIC EMISSION SPECTROSCOPY. PREPARATION

SAMPLE PREPARATION. ELEMENTAL ANALYSIS

INTRODUCTION

Nowadays most of the chemical analyses to determine the constituent elements of a sample are

approached by absorption or atomic emission spectroscopy, x-ray fluorescence or electrochemical

techniques, although traditionally volumetric, gravimetric, ultraviolet-visible spectroscopy,

fluorescence spectroscopy and molecular phosphorescence have been used, by direct or indirect

methods. The characterization of a material by atomic absorption or emission spectroscopy goes

through a fundamental stage of enormous repercussion in the result of the analysis, such as sample

preparation. This chapter begins with the development of absorption and atomic emission

spectroscopy, since the book deals with the techniques of analysis and characterization, even

though it is known that the logical and practical order is to deal with sample preparation at the

beginning. Atomic absorption spectroscopy is based on the absorption of radiation by free atoms

in the ground state, while atomic emission spectroscopy studies the emission of radiation by free

atoms or ions in the excited state.

If only alcohol was burned, this emission disappeared. In 1860, he demonstrated the presence of

certain elements in the solar atmosphere, related the phenomena of absorption and emission, and
deduced that each element has a characteristic spectrum. Shortly thereafter, in 1861, together with

Bunsen and Fraunhofer, he established the foundations and usefulness of a new method of

spectrochemical analysis, assuming that the fine lines of both emission and absorption are

generated by atoms. Corroborating these studies, in 1873, Champion, Pellett and Grenier carried

out the first quantitative determinations of sodium by flame emission as outlined by Talbot forty-

seven years earlier.

The first experiments demonstrating the relationship between emission and absorption were

carried out by Wood in 1902. Smith's studies of indium, aluminum, gallium and thallium, Hughes

and Thomas perfected studies of mercury vapor in air by atomic absorption and, finally, Lunegardh

demonstrated the versatility of flame-emission spectroscopy. The first real applications of atomic

absorption spectroscopy appeared in 1955 by Alan Walsh and Alkemade. Shortly thereafter, in

1960, the first atomic absorption spectrometry instrument was commercialized.

FUNDAMENTALS OF THE TECHNIQUE

Chemical analysis: atomic absorption and emission spectroscopy. An atom in its ground state is

subjected to the action of electromagnetic radiation in such a way that an electron at an energy

level E 0 can absorb the energy associated with this radiation and move to a higher energy level E

1, leaving the atom in an electronically excited state.

ach element has a unique electronic structure that characterizes it, and its orbital configuration is

complex, so that there are many possible electronic transitions, each of which corresponds to the

absorption or emission of radiation of a certain frequency (Figure 6.2).

frequency (Figure 6.2), i.e., between different energy states:

M 0 + hvl + hv2 + hv3 + ... ^ M*

These radiations absorbed by the atoms in the excitation process or emitted in the relaxation

process can be quantified for analytical purposes.

in the relaxation process can be quantified to be used for analytical purposes; for this, it is necessary

to have the element M in the form of an atom, either in its fundamental state or in its excited state.

state or in its excited state, which is achieved by means of an energetic input through a flame

This is achieved by means of a flame, a graphite homo, an electric arc, a spark, a plasma, etc. Since

the transform ationM0 ^ M* is a reversible equilibrium, it can be shifted in one direction or the

other.

the amount and form of the energy supplied, i.e., it can move in one direction or the other.

that is supplied, i.e., as a function of the ratio between the population of atoms in the ground state

M 0 and the excited state M 0.

in the fundamental state M 0 and excited M * according to the Boltzmann equation:

PEAK BROADENING

- Doppler effect. The wavelength of the radiation emitted or absorbed by a moving atom decreases

as it moves toward the detector and increases as it moves away from it. The maximum Doppler

shift is exhibited by atoms moving at the highest velocities and in line with the detector. The

perpendicular movements of the atoms do not contribute, therefore, the wavelength distribution

that reaches the detector is symmetrical.

Doppler shift, directly related to temperature, as occurs inside the flames, is due to the fact that the

individual atoms present a statistical distribution of Maxwell-Boltzmann velocities, the

frequencies reaching the detector show an approximately symmetrical distribution, with a

maximum corresponding to a Doppler shift of zero. It is the result of collisions between the

absorbing or emitting species with other atoms or ions present in the medium or even with atoms

of the same element. These collisions cause small changes in the atomic energy velocities and,

consequently, a dispersion of the emitted or absorbed wavelengths is caused. The broadening due

to this effect is of the same order of magnitude as that produced by the Doppler effect.

INSTRUMENTATION
An atomic absorption spectroscopy or atomic emission spectroscopy instrumentation should

consist of a radiation generating system characteristic of the element to be analyzed (the excited

element itself in atomic emission spectroscopy) and a mechanism to obtain the radiation.

atomic emission spectroscopy should consist of a system generating radiation characteristic of the

element to be analyzed (the excited element itself in emission spectroscopy) and a mechanism for

obtaining atoms in the ground state in the case of absorption spectroscopy.

in the case of absorption spectroscopy.

The wavelength at which absorption or emission occurs appears surrounded by the rest of the

multi-wavelength radiations escaping from each element; therefore, a monochromatization system

is required to isolate a certain characteristic radiation. These radiations have to be conducted from

the

These radiations must be conducted from the collection system to the monochromator and from

the monochromator to the detector,

This requires an optical system, consisting of lenses, mirrors, slits, etc., more or less complex

depending on the performance required.

depending on the required performance of the equipment.

The resulting radiation must be detected, amplified and measured by means of the components of

the

the components of the electronic system.

The whole of all this constitutes the measuring equipment.

EQUIPMENT COMPONENTS

- Radiation production medium characteristic of the element to be analyzed. It is

exclusive of atomic absorption spectroscopy.

- Introduction device of the sample to be analyzed.

- Atomization and excitation mechanism.

- Monochromatization system.

- Spectral background correction systems.

- Radiation detection, amplification and measurement system.

Hollow cathode lamp

It consists of an anode, usually a tungsten wire 1 mm in diameter and 30-40 mm long, and a cathode

located in the optical axis of the system, in the form of a hollow cylinder of 5-6 mm in diameter

and made of the element to be analyzed. Both are placed inside a glass tube in which there is a

noble gas at a pressure of less than 10 mm of mercury.

Ar ^ Ar+ + le-
ELECTRODELESS DISCHARGE LAMP

The electrodeless discharge lamp is of a more complex design, the element or a salt of it is placed

in a small quartz bulb with a low pressure argon atmosphere. This movement of ions and electrons

causes a heating of the ionized gas sufficient to drive the element to its excited state.

These lamps are used almost exclusively for those elements which, because they are very volatile,

do not allow the use of a hollow cathode lamp or are rapidly exhausted, such as arsenic, bismuth,

cadmium, lead, antimony, selenium, stannous, etc. The sensitivity they offer is higher than hollow

cathode lamps for these same elements and their lifetime is longer, but they have some

disadvantages such as lower stability, slow heating, wider emission lines, need for a

radiofrequency source which makes the product more expensive.

SAMPLE INTRODUCTION DEVICE
LIQUID SAMPLES

The sample to be analyzed is usually in a liquid state and is introduced by means of a nebulization

system, which consists of two components: the nebulizer and the nebulization chamber. The

purpose of the spray chamber is to homogenize and even reduce the size of these droplets, as well

as to select the finest and most uniform fraction of the aerosol, which constitutes the secondary

aerosol.

They consist of a fine capillary through which the sample is sucked, either by Venturi effect or by

means of a peristaltic pump, meets a gas flow at high velocity to form an aerosol.

NEBULIZERS

They introduce variable sample flows, give stability to the plasma and condition the accuracy and

detection limit of the

the precision and detection limit of the measurement.

Pneumatic nebulizers. They use a high velocity gas flow to produce the aerosol. They are the most

widely used and there are two designs: cross-flow nebulizers and concentric nebulizers.

MIST CHAMBERS

Pneumatic nebulizers produce aerosols with very heterogeneous droplet size distributions; the mist

chambers favor the reduction of droplet sizes and select the smallest droplets to be introduced into

the plasma dragged by a carrier gas, which in turn sends the larger ones to the drain.

In these chambers the larger droplets that form part of the aerosol fall to the bottom to be eliminated

by the drainage and the smaller ones are dragged by the auxiliary gas to the plasma; they are also

frequently called Scott double-passage chambers. These conical centrifugation chambers, which

provide high efficiency, are named after the helical movement of the aerosol made up of the lighter

droplets until they reach the plasma.

Graphite chamber
The graphite chamber constitutes the electrothermal atomization system and consists of a small

hollow graphite tube 20-30 mm long and 5-10 mm in diameter, with a hole through which the

sample solution or suspension is introduced.

diameter, with an orifice through which the sample in solution or suspension (1-100 ^1) is

introduced

(1-100 ^1) is introduced through a micropipette or an automatic injector. The radiation from the

lamp passes through it along its longitudinal axis (Figure 6.15). Metra Monochromator Detector

8m_______

Figure 6.15. Schematic of experimental device with graphite tube.

A high electric current (several hundred amperes) is passed at low voltage (10 volts).

voltage (10 volts); since graphite is a poor conductor, applying current heats up the tube to a

temperature

the tube is heated to a temperature sufficient to atomize the sample. An inert gas flow is maintained

on the outside of the graphite tube, which prevents oxidation at high temperature, and on the inside

of the graphite tube, which prevents oxidation at high temperature.

oxidation at high temperature, and through the inside of the tube, to remove volatilized sample

components that may interfere with

volatilized sample components that may interfere with the measurement. The advantages are the

complete atomization of the

advantages are complete atomization of the sample, high residence times and avoidance of atomic

vapor dilution.
atomic vapor dilution with the flame-forming gases is avoided.

Chemical analysis: atomic absorption and emission spectroscopy. 221

The main disadvantage is the time required for the signal The main disadvantage is the analysis

time per sample, which can be as long as several per sample, which can take up to several minutes.

The entire atomization system is kept refrigerated for rapid cooling between each analysis.

The wide variety of applications for this vaporization system has made it necessary to develop

different types of different types of tubes have been developed to suit the nature of the different

samples.

different samples:

- Graphite Massmann tube: this is the standard tube, it is possible to introduce 5-100 ^l of sample.

5-100 ^l of sample, temperature gradients are generated between the center where the sample is

injected and the coldest ends that can lead to memory effects.

memory effects.

- Graphite tube with platform or mini-Massmann, due to its reduced diameter that allows to inject

smaller volumes, between 0.5-2 ^l of sample,

although there are modifications for larger volumes with larger diameter tubes that produce more

intense signals.

- Graphite rod: instead of being a hollow tube, a solid rod is used, in which recesses are made in

the tube for the in which recesses are made to house the sample; the profiles they present vary

according to the volume and the

The profiles they present vary according to the volume and characteristics of the sample to be

analyzed.

- It is common to coat the graphite tubes with a layer of pyrolytic graphite.

pyrolytic graphite, as the porosity of the graphite can cause problems during atomization. The

disadvantage of this is that it is more expensive and that the coating

degradation of the coating with use. By continuously adding a hydrocarbon mixture to the

hydrocarbon mixture to the purge gas can maintain the coating, but this procedure is incompatible

with the determination of some elements.

1. Drying stage

A temperature of 100-150 0C is maintained for 45-60 seconds in order to provoke the evaporation

of the solvent. evaporation of the solvent. The progressive heating avoids projections of the sample

inside the tube.

2. Mineralization stage
This stage aims to remove as many matrix interferents as possible, but without loss of analyte. The

dried sample is gradually heated at temperatures of 400-1,000 °C for 30-45 seconds to remove all

organic matter and decompose the inorganic matrix.

and decompose the inorganic matrix into a simple compound. The temperature of this stage should

not exceed the volatilization temperature of the compound.

3. Atomization stage High temperatures (2,000-3,000 °C) are reached in a short time (5-8 seconds)

to atomize the compound.

(5-8 seconds) to atomize the sample. This heating should be as fast as possible to ensure the

efficient and concentrated formation of the atomic vapor which can absorb or emit characteristic

radiation giving rise to signals which require a fast response electronic system electronic system,

since it must be able to follow the transient atomization process. transient atomization process.

4. Cleaning stage

The graphite chamber is subjected to higher temperatures than the atomization stage in order to

wash away the residues formed and thus avoid memory effects.
Cross-dispersion flat-grid monochromators

The dispersion achieved is very good, but has numerous overlapping orders.

TYPES OF EQUIPMENT

The techniques of atomic absorption spectrometry and inductively coupled plasma atomic

emission spectrometry with optical detection present different alternatives in terms of

instrumentation.

All configurations allow the quantitative determination of elements, although they differ greatly

in the way they approach this determination and in the number of elements and concentration range

they are capable of measuring.

 • Sequential Atomic Absorption Spectrometers (AA-SEC)

• Simultaneous Atomic Absorption Spectrometers (AA-SIM)

• Sequential Atomic Emission Spectrometers (ICP-SEC)

• Multichannel simultaneous atomic emission spectrometers (ICP-MUL)

• Simultaneous Atomic Emission Spectrometers (ICP-SIM)

OPERATIONAL PROCEDURE FOR INSTRUMENTAL MEASUREMENTS

Absorption and emission atomic spectroscopy are techniques that generally only require the

sample to be placed in solution and the measurements to be carried out under standard working

conditions. In some cases, due to the conditions of the elements to be determined, it is necessary

to use special working procedures to obtain a correct analysis.

to obtain a correct analysis: optimization of the sensitivity, improvement of the precision, increase

of the accuracy, etc., which is achieved by elimination or compensation of possible interferences

(Table 1).

compensation of possible interferences (Table 6.5), as well as good calibration.

calibration.
METHODOLOGY OF USE

When it is necessary to analyze the elements that compose a sample, one immediately thinks of

atomic absorption or emission spectroscopy. In plasma emission spectroscopy, baseline correction

is very important to integrate the signal, since spectral interferences can be frequent and a low

background is needed in the vicinity of the analytical peak.

APPLICATIONS OF THE TECHNIQUE

qualitative analysis

Atomic absorption and emission spectroscopy allow for qualitative analysis

although it is not its objective and, therefore, an excessive amount of time is spent in the sequential
sequential equipment, especially in the case of AAS-SEC, which involves changing the lamp for

each element.

element. In ICP-OES or simultaneous As equipment, it is much simpler to identify elements in a

short

identification of elements in a short interval of time.

Quantitative Analysis

Quantitative analysis is what has brought atomic absorption and emission spectroscopy into the

mainstream of laboratory techniques, making it, in most cases, indispensable. The simplest atomic

absorption equipment is capable of providing results of elemental compositions of any type of

sample with reproducibility, precision and accuracy, in a simple, fast and economical way,

characteristics difficult to achieve with any other instrumental technique. The quantification of an

element in the solution is carried out by the previous elaboration of the calibration line with the

most suitable standards, in number and concentration, using as blank the mixture used in the

dissolution of the sample, or the solvent of the solution.

COMPARISON OF THE DIFFERENT ATOMIC SPECTROSCOPY ATOMIC

SPECTROSCOPY TECHNIQUES

Atomic absorption spectroscopy techniques with flame (AAS-LL), with graphite chamber (AAS-

GF), with hydride generation (AAS-HG/AAS-vapor) and with graphite chamber (AAS-GF), with

hydride generation (AAS-HG/AAS-cold steam), atomic

plasma atomic emission (ICP-OES), plasma coupled to a mass spectrometer (ICP-MS) have mass

spectrometer (ICP-MS) have in common the determination of elements in solution.

The use of one or the other technique depends on the analytical characteristics, economic

conditions, availability and qualification of personnel.

The limits of detection condition the utilization of each spectroscopy:

SAMPLE PREPARATION

Samples can arrive at the laboratory in any of their states: solid, liquid and, less commonly because

of the difficulty involved in handling them, in gas form.

It is very common to emphasize the problems associated with the final stage of an analysis,

especially the measurement of some variable that may be related to the concentration of the

problem. The reality is that the complex work is focused, for laboratories in the diversity of new

materials, on current problems with legal limit values and compounds to be analyzed: inorganics;

organics; organometallics; numerous industrial products; pharmaceuticals; biological fluids and

tissues. With these substances, several steps must precede the final measurement, which is

generally the easiest to perform.

The difficulties encountered in the analysis of samples lie in their complexity or in the differences

in their composition, in the precision required, the time required or available, the number of

samples/day processed, the methodology to be followed, which often requires adapting existing

procedures, if not changing them.

Pretreatments

Normally a series of operations or pretreatments are required, which offer a different

offer a different problem. In many cases some are not necessary and in others

others do not follow a defined order.

- Filtration of solid material in liquid samples.

- Crushing, sieving, homogenizing. Solid samples must be ground to homogenize the particle size.

This facilitates disintegration,

as it increases the contact surface and considerably reduces the time required for complete

dissolution.

necessary for complete dissolution.

The milling will be done manually or in different types of mills depending on the quantity and

type of sample

the quantity and type of sample, the desired particle size and the time employed.

This stage can be a source of errors due to:

- Changes in the chemical composition of the sample.

- Loss of sample components (heat generated during grinding).

- Contaminations (mortars, humidity, microbial...).

- Drying. Its purpose is to eliminate the water that is not part of the chemical constitution of the

sample.

chemical constitution of the sample. The adsorption, absorption and occlusion water is variable

with time

with time, which would change the percentages of all the components of the sample.

sample.

The adsorption water is usually removed at 105 °C. Preliminary studies with thermal analysis

(TGA) or differential thermal analysis (DTA) are performed to evaluate the best drying

temperature for the sample.

to evaluate the most suitable drying temperature at which stable weight is achieved.

stable weight.

Errors at this stage are due to:

- Incomplete elimination of different types of water.

- Changes in sample composition.

- Measurement (weight and/or volume) of the sample. Reference for the expression of the results.

results.

Transformation of the sample into a measurable species

Most atomic spectroscopic techniques require dissolution of the sample. The procedure will be

somewhat different for organic and inorganic analytes.

In general, different processes are involved such as disaggregation, dissolution, oxidation number

changes, separation techniques, addition of masking agents, modification of the characteristics of

the medium, preconcentration of the analyte...

Microwave digestion

Microwave radiation, which is used in this digestion technique, was described in the middle of the

20th century and the first equipment was commercialized around 1975 for domestic use and a

decade later at the laboratory level.

for domestic use and a decade later at the laboratory level, once the necessary measures were
and enabled the necessary safety measures. At present, there are ovens on the market that are

adapted to the requirements and needs of any laboratory, which allow the preparation of both

organic and organic samples.

preparation of both organic and inorganic samples and have a number of advantages over other

techniques.

a series of advantages over other more conventional preparation techniques, such as speed and

lower

cost-effectiveness, reproducibility of conditions, no loss of volatiles, no contamination, no

contamination

volatiles, no contamination, no fumes or vapors.

ELEMENTAL ANALYSIS
Carbon, hydrogen, nitrogen and sulfur are undoubtedly the elements of interest in most organic

the elements that are of interest in most organic applications. As we have already seen

previously seen, by atomic absorption and emission spectrometry it is impossible to see carbon

and hydrogen.

carbon and hydrogen, the quantification of nitrogen is practically impossible,

contamination is easy; on the other hand, sulfur can be quantified without problems by ICP-OES,

as long as

by ICP-OES, provided that a UV detector and an optics purged with inert gas are available (Figure

6.1).

with inert gas.

Carbon, hydrogen and nitrogen determination

The main method for the determination of carbon, hydrogen and nitrogen is the microcombustion

technique.
The analysis involves several stages

Degassing stage in which gases that may interfere with the determination are removed from the

pre-weighed sample. Combustion stage in pure oxygen flow at 900 0C. The possible combustion

products of an organic compound are carbon dioxide, water vapor, nitrogen, nitrogen oxides and

sulfur oxides. Sulfur, halogens and nitrogen interfere in the determination of carbon and hydrogen.

Carbon dioxide, nitrogen and water vapor formed are measured.

Sulfur determination

Sulfur determination follows the basic principles described for the analysis of carbon, hydrogen

and nitrogen. of carbon, hydrogen and nitrogen. The weighed sample, solid or liquid, is subjected

to an oxygen stream which The weighed sample, solid or liquid, is subjected to an oxygen stream

which oxidizes the organic matter to carbon dioxide (CO2), water, sulfur dioxide (SO2) and sulfur

trioxide (SO3). A temperature increase up to 1,350 °C ensures the shift to the formation of sulfur

dioxide (SO2).

The determination of sulfur after oxidation can be done by various methods:

infrared detector, a simple and direct method, or amperometric titration.

Oxygen determination

Oxygen determination is carried out in a quartz pyrolysis tube,

in helium atmosphere is heated to 900 °C, all the oxygen in the sample forms carbon monoxide

(CO), which is transformed into carbon dioxide (CO2) and measured as previously described.

is measured as described above.

Commercial equipment

There are commercially available equipment for macroanalysis, when the organic sample is large

and heterogeneous in nature, as well as for microanalysis.

and heterogeneous in nature, as well as for microanalysis when only a few milligrams are available

for elemental determination.

when only a few milligrams are available for elemental determination.

The determination of carbon, hydrogen, nitrogen, sulfur and oxygen is carried out in a few minutes

on commercially available

minutes in commercially available equipment; they are equipped with infrared cells for the

cells for the quantification of carbon, hydrogen, sulfur and oxygen and infrared cells.