Analytical Chemistry Chapter 3: Atomic Spectroscopy

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Questions and Answers

Atomic spectroscopy methods are categorized based on the ______ of atomization.

type

What is atomization?

Atomization is a process that converts molecular constituents (analyte) of a sample into atoms (and ions) in the gaseous state.

Which of the following are factors that contribute to atomic spectral line widths?

  • Natural Broadening (correct)
  • Collisional Broadening (correct)
  • Doppler Broadening (correct)
  • None of the above

The atomization process is the 'signal generator', meaning it produces the signal that is measured in atomic spectroscopy.

<p>True (A)</p> Signup and view all the answers

Which of the following are common atomization spectroscopic methods?

<p>Flame (A), Graphite Furnace (GF) or Electro-thermal Atomizer (B), Inductively Coupled Plasma (ICP) (C)</p> Signup and view all the answers

What are the advantages of using a flame atomization method?

<p>It introduces a relatively large and representative sample into the flame. (A), It is a simple and inexpensive technique. (B), It has a high temperature (2300 K), which is suitable for many applications. (C)</p> Signup and view all the answers

In the flame atomization method, the fuel/oxidant mixture affects the atomization temperature, meaning that different mixtures can be used to achieve different temperatures.

<p>True (A)</p> Signup and view all the answers

The ______ of a flame is a region where the primary combustion occurs, leading to the initial breakdown of the sample.

<p>base region</p> Signup and view all the answers

The ______ of a flame is a region where secondary combustion takes place, contributing to further breakdown of the sample and generation of atomic species.

<p>outer cone</p> Signup and view all the answers

Explain the process that occurs in the inner cone region of a flame.

<p>In the inner cone region of a flame, solid particles are carried by the air-fuel velocity. Atomization, excitation, and relaxation take place in this region.</p> Signup and view all the answers

In the graphite furnace atomization method, the atomization process and temperature are rigorously controlled using a series of heating steps, enabling optimized atomization and increased sensitivity.

<p>True (A)</p> Signup and view all the answers

What are the advantages of using a graphite furnace method for atomization?

<p>Enhanced sensitivity over flame atomization. (A), The entire sample can be analyzed. (B), Much of the background matrix can be eliminated. (C)</p> Signup and view all the answers

The atomization process in inductively coupled plasma (ICP) is achieved by using plasma, which is a high-temperature, ionized gas.

<p>True (A)</p> Signup and view all the answers

In the ICP atomization method, how does the sample interact with the plasma to achieve atomization?

<p>A stream of partially ionized argon gas is mixed with the nebulized sample solution, the gas is then passed through an induced magnetic field, and finally, the sample enters an emission region where it undergoes atomization and ionization. (A), The plasma interacts with the sample, causing the analyte atoms to undergo extreme resistive heating, resulting in atomization, ionization, and a more intense emission compared to flame methods. (B), The analyte atoms are heated to a high temperature by the plasma, leading to ionization and an increase in the intensity of the emitted light. (C)</p> Signup and view all the answers

What happens to the ions in the ICP atomization method?

<p>The ions couple with the magnetic field. The interaction between the ions and the magnetic field causes them to undergo extreme resistive heating, leading to atomization.</p> Signup and view all the answers

Atomic emission spectroscopy (AES) is a technique that measures the intensity of ______ emitted by excited atoms.

<p>light</p> Signup and view all the answers

Explain what atomic emission is.

<p>Atomic emission is the process where the relaxation of an excited species is accompanied by the emission of ultraviolet and visible light at discrete wavelengths (line spectra).</p> Signup and view all the answers

In atomic emission spectroscopy, the intensity of the emitted light is proportional to the concentration of analytes in the sample.

<p>True (A)</p> Signup and view all the answers

Explain the different stages of flame emission spectroscopy.

<p>Flame emission spectroscopy comprises four stages: evaporation, atomization, excitation, and emission of radiation. Evaporation involves sample dehydration by heat and solvent evaporation. Atomization reduces metal ions to metal atoms. Excitation is the process where electrons of metal atoms absorb energy from the heat of the flame. Finally, emission of radiation occurs when electrons in the excited state move back to the ground state, emitting the absorbed energy.</p> Signup and view all the answers

Flame photometers are equipped with a nebulizer and a burner, which together form a single unit.

<p>True (A)</p> Signup and view all the answers

Which of the following are advantages of using turbulent flow burners?

<p>They introduce a relatively large and representative sample into the flame. (A), They are considered to be a simple and inexpensive technique. (B), They operate at a high temperature. (C)</p> Signup and view all the answers

What are the disadvantages of using turbulent flow burners?

<p>They have a short path length, which can lead to the clogging of the tip. (A), They produce a noisy flame. (B), The sample is nebulized at the tip, which results in large and less well-atomized droplets. (C)</p> Signup and view all the answers

In direct insertion, the sample is introduced directly into the ______.

<p>flame</p> Signup and view all the answers

What are the advantages of using premix (laminar flow) burners?

<p>They have a long sample path length, effectively reducing the problem of clogging. (A), They produce a quieter flame. (B), The nebulization process occurs before the sample reaches the burner, which effectively removes large droplets at the mixing chamber. (C)</p> Signup and view all the answers

The disadvantage of using a premix burner is that it has a lower rate of sample introduction, potentially reducing the accuracy of sample representation in the flame.

<p>True (A)</p> Signup and view all the answers

What is the purpose of a wavelength selector?

<p>The purpose of a wavelength selector is to isolate a narrow wavelength band from the continuous wavelength of the electromagnetic spectrum, allowing for the selection of specific wavelengths for analysis.</p> Signup and view all the answers

Filters are used to select specific wavelengths in atomic emission or absorption spectroscopy.

<p>True (A)</p> Signup and view all the answers

The narrowness of the bandwidth results in ______ resolution.

<p>high</p> Signup and view all the answers

What is the main purpose of a detector in atomic spectroscopy?

<p>The detector in atomic spectroscopy is responsible for measuring the intensity of light emitted or absorbed by the analyte, which is directly related to its concentration in the sample.</p> Signup and view all the answers

What are some commonly used light sensors in atomic spectroscopy?

<p>Both A and B (C)</p> Signup and view all the answers

A detector is typically attached to an amplifier and an analog or digital readout device to process and display the measured signal effectively.

<p>True (A)</p> Signup and view all the answers

Atomic absorption spectroscopy (AAS) is a technique that measures the absorbance of light by ground state atoms.

<p>True (A)</p> Signup and view all the answers

What are the basic components of an atomic absorption spectrophotometer?

<p>All of the above (E)</p> Signup and view all the answers

The line source in AAS is a source of light that emits specific wavelengths corresponding to the analyte of interest.

<p>True (A)</p> Signup and view all the answers

What are the two main types of light sources commonly used in AAS?

<p>The two main types of light sources used in AAS are hollow cathode lamps (HCL) and electrodeless discharge lamps (EDL).</p> Signup and view all the answers

Hollow cathode lamps (HCL) are filled with an inert gas that is ionized using an applied potential of ~300 V DC, leading to the sputtered atoms of the analyte that produce light at specific wavelengths.

<p>True (A)</p> Signup and view all the answers

Explain how a hollow cathode lamp works.

<p>In a hollow cathode lamp, an applied potential ionizes the inert gas, causing positively charged ions to collide with the metal cathode, which is made of the analyte. This collision process sputters metal atoms into the gas phase, and a portion of these sputtered atoms are in excited states, emitting light at specific wavelengths when they relax back to the ground state. This emitted light is then used for absorption measurements in AAS.</p> Signup and view all the answers

Electrodeless discharge lamps (EDL) work on the principle of using a radio frequency or microwave field to excite atoms of the analyte within a sealed quartz tube, leading to the emission of light at specific wavelengths.

<p>True (A)</p> Signup and view all the answers

EDL lamps are generally more intense than HCL lamps, offering better sensitivity and making them a preferred choice for certain applications.

<p>True (A)</p> Signup and view all the answers

The disadvantage of EDL lamps is that they are unstable and only available for about 17 metals.

<p>True (A)</p> Signup and view all the answers

A chopper in atomic absorption spectroscopy is a rotating device that modulates the light beam from the hollow cathode lamp, helping to distinguish between the analyte's light absorption and background noise.

<p>True (A)</p> Signup and view all the answers

What is the purpose of background correction in atomic absorption spectroscopy?

<p>Background correction in atomic absorption spectroscopy is a technique used to mitigate the effect of background absorption, which can interfere with the measurement of analyte absorption. The correction process helps to isolate the analyte's absorption signal from the background, ultimately improving the accuracy and reliability of analytical results.</p> Signup and view all the answers

In atomic absorption spectroscopy, the monochromator is a component that is placed between the flame and the detector.

<p>True (A)</p> Signup and view all the answers

What is the primary role of the monochromator AAS?

<p>All of the above (D)</p> Signup and view all the answers

Monochromators are typically made up of three parts: an entrance slit, a dispersing element, and an ______ slit.

<p>exit</p> Signup and view all the answers

What are some common examples of dispersing elements used in monochromators?

<p>Both A and B (C)</p> Signup and view all the answers

What is the role of the detector in AAS?

<p>The detector in AAS is responsible for converting the light that passes through the monochromator into a measurable electrical signal. This signal is then processed to determine the absorbance of the light, which is directly related to the concentration of the analyte in the sample.</p> Signup and view all the answers

What are the main types of detectors used in AAS?

<p>Both of the above (C)</p> Signup and view all the answers

The main advantage of AAS is its ability to determine the concentration of over 60 elements in a sample, making it a widely used technique in various analytical applications.

<p>True (A)</p> Signup and view all the answers

AAS is also known for its speed of routine analysis, as measurements can be performed quickly.

<p>True (A)</p> Signup and view all the answers

Another advantage of AAS is its minimal clogging problems, making it a reliable technique with reduced downtime.

<p>True (A)</p> Signup and view all the answers

The main disadvantage of AAS is its lower sensitivity compared to other methods, such as flame photometry, limiting its application for analyzing very low concentrations of analytes.

<p>True (A)</p> Signup and view all the answers

What are the main types of interferences common in atomic spectroscopy?

<p>Both A and B (C)</p> Signup and view all the answers

Blank interferences refer to interferences that are caused by the sample matrix itself, while analyte interferences are caused by the analyte's interaction with the sample matrix.

<p>False (B)</p> Signup and view all the answers

What are the main types of analyte interferences?

<p>All of the above (D)</p> Signup and view all the answers

Spectral interferences occur when the absorption or emission spectra of an interfering species overlaps or lies close to that of the analyte.

<p>True (A)</p> Signup and view all the answers

Physical interferences are mainly caused by changes in the viscosity of the sample due to the presence of certain substances, which can influence the flow rate and nebulization efficiency.

<p>True (A)</p> Signup and view all the answers

Chemical interferences arise when species present in the sample matrix interact with the analyte, modifying its atomization behavior and affecting its signal.

<p>True (A)</p> Signup and view all the answers

During chemical interferences, the presence of certain species in the sample matrix can either enhance or decrease the volatility of the analyte, significantly impacting its atomization and influencing the analysis.

<p>True (A)</p> Signup and view all the answers

Ionization interferences arise when the presence of easily ionized elements, such as alkali and alkaline earth metals, in the sample can alter the ionization behavior of less-easily ionized elements, influencing the analysis.

<p>True (A)</p> Signup and view all the answers

One common solution to manage ionization interferences is to use ionization suppressants, which are elements that have a lower ionization potential than the analyte, suppressing the ionization of the analyte and improving the accuracy of the analysis.

<p>True (A)</p> Signup and view all the answers

When using a hotter flame in atomic spectroscopy, the analyte is more likely to be atomized, reducing the effect of chemical interferences.

<p>True (A)</p> Signup and view all the answers

Protective agents are compounds that form stable but volatile complexes with analyte ions, preventing them from interacting with the sample matrix and reducing the potential for chemical interferences.

<p>True (A)</p> Signup and view all the answers

Releasing agents are compounds that preferentially react with interfering anions, preventing them from inhibiting the atomization of the analyte, and improving the accuracy of the analysis.

<p>True (A)</p> Signup and view all the answers

Flashcards

Atomization

A process that converts molecular components of a sample into atoms (and ions) in the gaseous state.

Atomic Emission Spectrometry (AES)

A type of atomic spectroscopy where the emission of light from excited atoms is measured to determine the concentration of the analyte.

Atomic Absorption Spectrometry (AAS)

A type of atomic spectroscopy where the absorption of light by atoms in their ground state is measured to determine the concentration of the analyte.

Flame Atomization

A method of atomization in which the sample is introduced into a flame, producing high temperatures for atomization and excitation.

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Graphite Furnace (GF) Atomization

A method of atomization that uses a graphite furnace to heat the sample, achieving a high temperature for atomization.

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Inductively Coupled Plasma (ICP) Atomization

A method of atomization that utilizes an inductively coupled plasma (ICP) to generate a high-temperature plasma for atomization and excitation.

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Relaxation

The tendency of excited atoms to lose energy and return to their ground state, releasing light at a specific wavelength.

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Excitation

The process by which an atom absorbs energy from a light source and moves to a higher energy state.

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Spectral Line Width

The width of a spectral line, which is influenced by factors like natural broadening, collisional broadening, and Doppler broadening.

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Spectral Interference

A type of interference where the absorption or emission spectra of an interfering species overlaps or lies close to that of the analyte, causing inaccurate measurements.

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Chemical Interference

A type of interference where the chemical environment in the sample affects the atomization process of the analyte, leading to inaccurate results.

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Ionization Interference

A type of chemical interference where the presence of easily ionized elements in the sample affects the ionization of the analyte.

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Nebulizer

A device used in atomic spectroscopy to convert a sample solution into a fine aerosol spray.

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Hollow Cathode Lamp (HCL)

A light source commonly used in AAS that emits a specific wavelength of light corresponding to the analyte.

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Electrodeless Discharge Lamp (EDL)

Another type of light source used in AAS that emits a more intense light compared to HCLs.

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Background Correction

The process of removing unwanted radiation from the light beam before it reaches the detector in AAS.

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Wavelength Selector

A device used in AAS to select a specific wavelength of light emitted by the source, allowing only the desired wavelength to pass through to the detector.

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Detector

A component in AAS that detects the amount of light that passes through the flame or furnace.

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Premix (Laminar Flow) Burner

A type of burner in flame AAS that mixes the fuel and oxidant before combustion, resulting in a more stable and quieter flame.

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Turbulent Flow Burner

A type of burner in flame AAS that introduces the sample directly into the flame, resulting in a more rapid but less controlled atomization.

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Releasing Agent

A substance added to a sample in AAS to reduce the effect of chemical interferences by preferentially reacting with the interfering anions.

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Protective Agent

A substance added to a sample in AAS to reduce the effect of chemical interferences by forming stable and volatile compounds with the analyte ions.

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Detection Limit

The minimum concentration of an analyte that can be detected by a specific analytical method.

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Zeeman Effect Background Correction

A method of increasing the sensitivity of AAS by using a high-intensity light source that minimizes the effect of background absorption.

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Emission Intensity

The measurement of the intensity of light emitted by a sample in AES.

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Absorbance

The measurement of the amount of light absorbed by a sample in AAS.

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Sample Preparation

The process of removing any chemical components from a sample that might interfere with the analysis.

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Deuterium Background Correction

A technique used in AAS to compensate for spectral and chemical interferences by measuring the absorbance at two wavelengths corresponding to the analyte and a reference wavelength.

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Study Notes

Analytical Chemistry - Chapter 3: Atomic Spectroscopy

  • Course Name: Analytical Chemistry
  • Chapter: 3 - Atomic Spectroscopy
  • Outline:
    • 3.1. Types of Atomic Spectroscopy - AES and AAS (Flame, GF, ICP) and atomization methods
    • 3.2. Atomization process and different atomization methods (Flame, GF, ICP)
    • 3.3. Atomic Emission Spectroscopy - Flame AES instrumentation, advantages and drawbacks
    • 3.4. Atomic Absorption Spectroscopy - instrumentation, advantages and drawbacks
    • 3.5. Spectral interferences in AAS
    • 3.6. Safety precautions
    • 3.7. Detection limits for atomic spectroscopy
  • Types of Atomic Spectroscopy: Emission and Absorption Spectrometry.
    • Atomization is a process that converts molecular constituents (analyte) in a sample to atoms (and ions) in the gaseous state. It is the signal generator.
  • Factors contributing to atomic spectral line widths: Natural, Collisional, and Doppler Broadening.
  • Atomization Process
    • Different methods for atomization include flame, graphite furnace (GF), and inductively coupled plasma (ICP).

Types of Atomization Spectroscopic Methods

  • Flame Atomization: Different fuel/oxidant mixtures achieve varying atomization temperatures.
    • Examples include
      • Gas/Air (1700-1900°C)
      • Gas/O2 (2700-2800°C)
      • H2/Air (2000-2100°C)
      • etc.
  • Graphite Furnace (GF) Atomization: Atomization is achieved through a series of controlled heating steps (typically 10-50 μL). The entire sample is analyzed, and background matrix interference is reduced.
  • ICP (Inductively Coupled Plasma) Atomization: Atomization is achieved using plasma (about 6000 K). Ionization and emission are more intense than in a flame method.

Atomic Emission Spectroscopy (AES)

  • Instrumentation: Includes a source, wavelength isolation device, transducers, signal processing and a computer system. Sample is nebulized and converted into aerosol.
  • Process in a flame:
      1. Evaporation: sample dehydration by heating and solvent evaporation.
      1. Atomization: metal ions are reduced to metal atoms.
      1. Excitation: electrons absorb energy from the flame heat.
      1. Emission of radiation: electrons return to ground state, releasing absorbed energy as light.
  • Advantages: Simple and cheap instrumentation, sensitive.
  • Disadvantages: Limited application

Flame Atomic Emission Spectroscopy: Instrumentation

  • Schematic Diagram: Shows elements for sample introduction, light source, wavelength selector, detector.

Atomic Absorption Spectroscopy (AAS)

  • Basic Components: includes a light source (hollow cathode lamp), atomizer, monochromator, detector. Reference beam and chopper are also part of the system.
  • Source of Radiation in AAS:
    • Hollow Cathode Lamps (HCL)
    • Electrodeless Discharge Lamps (EDL)

HCL (Hollow Cathode Lamps)

  • Characteristics: Exit window construction of pyrex or quartz

  • Filled with an inert gas (Ne or Ar), at a low vacuum (1-5 torr)

  • Applications for spectral measurements of light emission from atoms.

  • Light intensity limitations: sputtered cations redeposit on cathode surface, causing self-absorption

  • The light source from a HCL emits light at a specific wavelengths for spectral identification.

  • Different types of interference

  • Spectral Interference: Involves overlap of the analyte's spectrum with interfering species.

  • Physical Interference: Changes in sample viscosity can affect the flow rate and nebulization efficiency/

  • Chemical Interference: Interfering species in the sample matrix can alter atomization behaviour of analyte. Ionization.

  • Detection limits: Different methods for atomic spectroscopy (Flame AA, Electrothermal AA, Flame Emission, ICP Emission, ICP-MS).

  • Safety Precautions: Acetylene gas is highly flammable and needs safe handling.

  • Solutions for Spectral and Chemical Interferences:

    • Use of protective/releasing agents
    • Using different oxidant/fuel mixtures
    • Corrections.

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