pg 438, 450-453
Introduction to Forensic Science
Absorption and Emission Spectra
- Presence of absorption and emission spectra for various gaseous elements: Sodium, Nitrogen, Hydrogen, Oxygen.
- Graphical representation: absorption and emission ranges from 450 nm to 700 nm.
- 450 nm: blue range
- 550 nm: green range
- 600 nm: orange range
- 650 nm: red range
Atomic Spectroscopy (Section 12.3)
12.3.1 Introduction
- Forensic scientists help solve analytical questions:
- Chemical composition of samples.
- Identifying mixtures vs. pure substances.
- Quantifying components in samples.
- Spectroscopic methods provide rapid answers:
- Useful for determining elemental composition of substances.
- Understanding the elemental makeup aids in tracing origins and identities of forensic samples.
Types of Analytical Information:
- Qualitative Data: Indicates if a specific component exists in the sample.
- Example: Detection of arsenic in food, lead in paint, and iron in inks.
- Quantitative Data: Measures the amount of a component present.
- Examples include:
- Analyzing alloy in crime scene bullets vs suspect's gun.
- Determining cocaine concentration in seized samples.
- Assessing beryllium levels in tissue samples for cause of death.
- Atomic spectroscopy focuses on identifying and quantifying elements in samples through light interactions.
Key Terms in Spectroscopy:
- Ground State: Lowest energy state of an atom or molecule.
- Excited State: Higher energy states of an atom or molecule than the ground state.
- Emission: Transition where an electron falls from a higher energy state to a lower state, emitting light.
- Absorption: Transition where an electron is promoted from a lower energy state to a higher state by absorbing energy.
Example of Molecular Spectroscopy:
- Hydrogen Molecule (H₂): Contains two electrons in the lowest bonding molecular orbital.
- Electrons must fill molecular orbitals based on quantum mechanics, with only two per orbital.
Ultraviolet-Visible Spectroscopy (Section 12.4.2)
- Encompasses the ultraviolet to visible spectrum (150 nm to 750 nm), sufficient for electron transitions within molecules (electronic spectroscopy).
- Photon Absorption: Electrons transition from lower energy states (ground state) to higher states.
- Emission: Similar to atomic spectra where electrons emit photons transitioning from high to low energy states.
Practical Applications:
- Forensic analysis often employs UV-visible spectroscopy to identify organic compounds' functional groups.
- Certain groups absorb specific light wavelengths:
- For example: Aliphatic bromides absorb light around 205 nm; C=O units absorb around 290 nm.
- Identifying functional groups aids in recognizing compound identity and concentration in forensic samples.
- Color analysis in forensic investigations of paints, clothing, and other colored materials is facilitated by UV-visible spectroscopy.
- Rather than describing a color, forensic analysis can specify absorption peaks (e.g., absorption at 510 nm indicates a specific red from another red absorbing at 520 nm).
Infrared Spectroscopy (Section 12.4.3)
- Deals not with electronic transitions, but with vibrational transitions due to infrared radiation, which has longer wavelengths than visible light.
- Infrared energy excites quantized vibrations in chemical bonds, similar to compressing springs.
- Vibrational Energy: Tied to the strength of the chemical bond and affected by factors like atomic identity and bonding types:
- Example of CO₂ regarding vibrational energy states.
- To absorb infrared light, a change in the electronic center of charge must occur.
Vibrational Modes of CO₂:
- Vibrational States:
- Symmetric Stretch: O atoms move in/out simultaneously.
- Asymmetric Stretch: One O moves closer to C while the other moves away. This change allows absorption of IR light.
- Bending Modes: Similar to stretching, involve physical movement without bond breaking, also allow for IR absorption.
- The IR spectrum shows only absorptions corresponding to allowed vibrations, showing that CO₂ is a simple molecule with specific vibrational characteristics.
Applications in Forensic Science:
- Spectroscopy can enhance forensic methods, enabling identification of colors in various materials and detecting adjustments and restorations in fine artworks, establishing provenance and authenticity.
- Example: Analysis of works by Dirck Bouts reveals retouching through spectral techniques, allowing restorers insights into restoration needs.