Chapters 4-6 * Unit 3: Part 1 * Unit 3: Part 1 DO NOW: What is glass ? Homework: Complete Pre-lab assignment. Today students will: * Determine which chemical and physical properties provide distinguishing characteristics of matter * Determine procedure for analysis of glass fragments * Develop an investigation plan to recognize differences in glass fragments * *The forensic scientist must determine the properties which give distinguishing characteristics to matter, allowing for a unique identity. *Physical properties such as weight, volume, color, boiling point, and melting point describe a substance without reference to any other substance. *A chemical property describes the behavior of a substance when it reacts or combines with another substance. * *Temperature is a measure of heat intensity, or the hotness or coldness of a substance. * In science, the most commonly used temperature scale is the Celsius scale. This scale is derived by assigning the freezing point of water a value of 0°C and its boiling point a value of 100°C. *Weight is the force with which gravity attracts a body. *Mass refers to the amount of matter an object contains independent of gravity. *The mass of an object is determined by comparison to the known mass of standard objects. * *Density: (D = M/V) *Density is an intensive property of matter, meaning it remains the same regardless of sample size. *It is considered a characteristic property of a substance and can be used as an aid in identification. * * Put water into the beaker until it is ½ full * Place a pen or pencil into the water * Observe what happens to the pen/pencil * Make notes in your notebook * Answer the following questions: * Why do you think this happens? * What is happening to create this effect? * Would using a different liquid cause a different effect? * Could this property be used to identify or compare glass samples? * Explain * * Explain your observations * Offer possible explanations * *Silently read background info. (12 min) *In small groups discuss answers to the following question: (7 min) *Define refraction and refraction index *Explain how this property can be used to identify class evidence *Which other properties of glass will be used, distinguish chemical and physical properties * *Define refraction and refraction index *Explain how this property can be used to identify class evidence *Which other properties of glass will be used, distinguish chemical and physical properties * * Names of lab partners * Question you will be investigation * Background information summary, most important to investigation * Hypothesis * Explanation of the procedures to be followed in the lab (must be in your own words, what will you do?) VIP: A completed pre-lab is your entrance ticket into the experiment, without it you will not be allowed to begin working in the lab! * Today students will: * Determine which chemical and physical properties provide distinguishing characteristics of matter * Define refractive index. * Distinguish crystalline from amorphous solids. * Define double refraction and birefringence. * Describe the dispersion of light through a prism * Determine how glass samples are analyzed * *Light waves travel in air at a constant velocity until they penetrate another medium, such as glass or water, then they are suddenly slowed *This causes the rays to bend. *The bending of light waves because of a change in velocity is called refraction. *Refractive index :the ratio of the velocity of light in a vacuum to the velocity of light in the medium under examination. * *Example: at 25oC the refractive index of water is 1.333. *This means that light travels 1.333 times faster in a vacuum than it does in water at 25oC. *Like density, refractive index is an intensive property and will serve to characterize a substance. * * *Glass is a hard, brittle, amorphous substance that is composed of silicon oxides mixed with various metal oxides. *Amorphous solids have their atoms arranged randomly, unlike crystals. *Tempered glass is stronger than normal glass due to rapid heating and cooling. *Laminated glass found in car windshields has a layer of plastic between two pieces of ordinary window glass. * CRYSTALLINE SOLIDS * Crystalline solids have the following fundamentals properties. * 1. They have characteristic geometrical shape. * 2. They have highly ordered three-dimensional arrangements of particles. * 3. They have sharp melting and boiling points. * Examples: * Copper Sulphate (CuSO4), NiSO4, Diamond, Graphite, NaCl, Sugar etc * AMORPHOUS SOLIDS * Solids that don’t have a definite geometrical shape are known as Amorphous Solids. * 1. In these solids particles are randomly arranged in three dimension. * 2. They don’t have sharp melting points. * 3. Amorphous solids are formed due to sudden cooling of liquid. * 4. Amorphous solids melt over a wide range of temperature * 5. Examples: Coal, Coke, Glass, Plastic, rubber etc * *For the forensic scientist, the problem of glass comparison is one that depends on the need to find and measure those properties that will associate one glass fragment with another while minimizing or eliminating other sources. *To compare glass fragments, a forensic scientist evaluates two important physical properties: density and refractive index. * Today students will: *Define double refraction and birefringence. *Describe the dispersion of light through a prism *Determine how glass samples are analyzed *Define the Becke line * * *The flotation method is a rather precise and rapid method for comparing glass densities. *In the flotation method, a glass particle is immersed in a liquid. *The density of the liquid is carefully adjusted by the addition of small amounts of an appropriate liquid until the glass chip remains suspended in the liquid medium. *At this point, the glass will have the same density as the liquid medium and can be compared to other relevant pieces of glass which will remain suspended, sink, or float. * *Crystalline solids have definite geometric forms because of the orderly arrangement of their atoms. *These solids refract a beam of light in two different light-ray components. *This results in double refraction. *Birefringence is the numerical difference between these two refractive indices. * Not all solids are crystalline in nature. For example, glass has a random arrangement of atoms to form an amorphous or non-crystalline solid. * * http://Birefringence * *The flotation and the immersion methods are best used to determine a glass fragment’s density and refractive index, respectively. *The latter involves immersing a glass particle in a liquid medium whose refractive index is varied until it is equal to that of the glass particle. *At this point, known as the match point, the Becke line disappears and minimum contrast between liquid and particle is observed. *The Becke line is a bright halo near the boarder of a particle that is immersed in a liquid of a different refractive index. * *The flotation and the immersion methods are best used to determine a glass fragment’s density and refractive index, respectively. *The immersion method: involves immersing a glass particle in a liquid whose refractive index is changed until it is equal to that of the glass particle. *At this point, known as the match point, the Becke line disappears and minimum contrast between liquid and particle is observed. *The Becke line is a bright halo near the boarder of a particle that is immersed in a liquid of a different refractive index. * * *Refractive Index of Glass * Uses Becke Line - a bright halo of light that appears around the perimeter of a particle when the indices of refraction of the particle and surrounding medium are different. Glass has higher refractive index Becke line seen inside Rays converge RI(glass) > RI(solvent) Glass has lower refractive index Becke line seen outside Rays diverge CHE 113 30 RI(glass) < RI(solvent) * Refractive Index of Class 1. Hot stage microscope used 2. Glass is immersed in RI liquid which is higher RI than glass. Temperature is raised until Becke line disappears. Rate of change of RI in liquid is known (3x10-4/degree) so the RI of the unknown can be determined 3. The point where the Becke line disappears: RI of the sample = the RI of the liquid *The penetration of window glass by a projectile, whether it is a bullet or a stone, produces cracks which radiate outward (radial fractures) and encircle the hole (concentric fractures). *By analyzing the radial and concentric fracture patterns in glass, the forensic scientist can determine the direction of impact. * * Two kinds of fractures, radial fractures (those radiating from the center) and concentric fractures. * CHE 113 33 * The direction of force in breaking a window pane can be determined by the direction of the rib marks (stress marks left on broken edges of glass that are perpendicular to one side and that curve tangentially, run almost parallel, to the other side). * * On radial fractures (those radiating from the center) the direction of the force is on the same side as the tangential (almost parallel) parts of the rib marks. * The edge of the glass where the rib lines are perpendicular is not the side of the glass that the force came from. This is the little R rule—radial cracks make right angles to the rear. * * On concentric fractures, the perpendicular part of the rib mark is the side from which the breaking force came. The rib fractures DO make a right angle to the side the force came from. * If you’re standing inside and break a pane of glass, most of the glass will land outside— but some will fly backwards towards you, landing inside the house and depositing tiny shards on your clothing. * * Concentric Crack Radial Crack Radial cracks make Right angles to the Rear. CHE 113 37 * Area on a windshield where the wiper blades cross Area on a windshield where only one wiper blade sweeps Scratches on a side window from grit caught in the rubber *A high-velocity projectile such as a bullet often leaves a hole that is wider at the exit side, and hence its examination is important in determining the direction of impact. *The direction of impact can also be accomplished by applying the 3R Rule: Radial cracks form a Right angle on the Reverse side of the force. *The sequence of impacts when there have been successive penetrations of glass is frequently possible to determine because a fracture always terminates at an existing line of fracture. * * * If a window is broken by a bullet, it is possible to determine the bullet's direction by noting the side of the cone-shaped hole left by the bullet. The small opening is on the entrance side and the large opening is on the exit side. * A determination of the sequence of bullet holes can be made by noting the radial fractures. Radial fractures caused by the passage of a bullet will stop at any pre-existing fracture. * * A bullet makes a clean-cut hole in the side of entrance and causes a saucer-shaped or coning depression on the exit side, with a greater diameter than the entrance hole. * Glass fractures caused by a blunt object will show a pattern of fractures like, but not as regular as, the pattern from a bullet. * Fractures due to heat are wave-shaped. They do not show a regular pattern of radial and concentric lines like fractures caused by impact. *If even the remotest possibility exists that glass fragments may be pieced together, every effort must be made to collect all the glass found. *When an individual fit is thought improbable, the evidence collector must submit all glass evidence found in the possession of the suspect along with a representative sample of broken glass remaining at the crime scene. * *The glass fragments should be packaged in solid containers to avoid further breakage. *If the suspect’s shoes and/or clothing are to be examined for the presence of glass fragments, they should be individually wrapped in paper and transmitted to the laboratory. * *Physical Measurements and Chemical Composition of Glass: * Density * Refractive Index (most glass is the same - but can tell if two samples are different) * Polarizing Microscopy (determine tempered glass) * IC-MS (inductively coupled mass spectrometer) * *Physical Measurements and Chemical Composition of Glass: * Density *Floatation Method *Gradient Tubes *Volumetric Measurements (mass measurement and volume by displacement) * * Sequence the fractures on the given hand outs * * Do Now: How can soil play a role in a forensic investigation? Today students will: * List the important forensic properties of soil. * Explain soils analysis techniques * Describe the proper collection of soil evidence * Analyze several important cases in which soil evidence played a major role * * *Mixture of organic and inorganic material *May range from 100% inorganic (sand) to nearly 100% organic (peat) *Inorganic part is minerals *Organic part is decayed plant and animal material and is sometimes called humus *Soil is class evidence - cannot be individualized to a particular location *There is no classification system for soils *Soils can be easily transported *Soils within a few meters horizontally or vertically differ * *Bulk analysis *Density gradient *Particle size distribution (sieving) *Inorganic components *Color (dissolve in water) *Petrography - mineral analysis; Requires a good deal of skill and practice * *Organic components *Liquid chromatography: separates into various components for identification of individual composition *Oxygen availability *Bacterial DNA? - Future possibility * * Soil is frequently found on clothing, shoes, or tools and in the wheel wells of vehicles. * Most soil analysis consists of comparing two or more samples by their mineral content, color, and density. The presence of pesticides and herbicides have also been used in soil comparison. * * Hit and Run: - Under-fender dirt/soil deposited at impact with the victim. matching the grease on the victim with the grease under the car. * Rape: - Soil on clothing of a suspected rapist placed suspect at the crime scene. * Murder: - Soil found on murder victims used to determine the location of homicides, especially when the murder occurs in one location and the body is then moved. Using water-current measurements, bodies/objects thrown into water can be located and where a discovered body/object originally entered the water determined. * Assault: - Identifying the type of rocks used as weapons led to the source of the rocks and helped locate suspects. * * Microscopic fossils called diatoms collectively deposited to form a sedimentary rock called diatomaceous earth. * Some manufacturers use diatomaceous earth for insulating safes. * Burglary crimes have been solved by examining white specks from suspects' hair and clothing to determine that the specks were actually diatoms that came from broken safes at crime scenes, and not dandruff as the suspects had claimed. * *Florida v. William Kennedy Smith *South Dakota v. Donald Eugene Moeller *Colorado v. Walter Osborne *The Death of a DEA agent – Enrico Camarena * *WKS accused of rape of Patricia Bowman *Alleged attack on grass lawn behind Kennedy estate in W. Palm Beach, Fl *WKS alleged consensual sex on the beach near estate *Jay Siegel used PLM(Polarized light microscopy)to compare samples from clothing of victim to lawn and beach areas *Samples consistent with beach, not lawn *WKS acquitted of rape * *Capital murder case of 9-year old Becky O’Connell on May 8, 1990. *Testimony by soil expert refutes defendant alibi *Victim snatched off street, raped, killed, body dumped in woods. *Suspicion fell on Defendant because of prior sex crime involvement. *Found guilty and sentenced to death. Appeal resulted in reversal owing to admission of evidence of prior bad acts. * * SD Supreme Court reversed and reinstated conviction * State geologist analyzed soil found in wheel wells of defendant pickup truck. Issue was whether soil came from crime scene South of Sioux Falls or from a road North of Sioux Falls where defendant claimed he was at time of crime * Geologist testified that soil could have come from crime scene. *Opinion based on: * Colors and general characteristics * Soil was much lighter or could not have come from other roads in area * “Sharp, clean” hornblende crystals much more likely to have come from crime scene area * *Part of appeal called for striking geologist’s testimony as being too speculative as to conclusions *At 2nd trial, geologist came into more evidence from scene and wheel well: dark green to black gahnite found at scene and in evidence from truck. This mineral extremely rare. * *Defense argued that geologist erred in identifying gahnite only by visual inspection. *Claimed that PLM should have been used (to confirm that gahnite is isotropic) and that x-ray diffraction should have been used to confirm. *Appeals court rejected appeal *There was no discussion at trial whether the finding of both hornblende and gahnite near Sioux Falls was a rarity or could be due to processing after mining elsewhere. * Bedrock of Sioux Falls contains neither hornblende nor gahnite. * *Osborne botches kidnapping of Adolph Coors from his ranch near Morrison and kills Coors *Ranch is near “Dakota Hogback” which is made of Dakota sandstone underlain by gray, green and maroon clay stones, shales, more sandstone and limestone. *Dirt road near ranch was essentially eroded, pulverized components of hogback. * * During kidnapping, a fight broke out and Osborne shot Coors. Fled in Osborne’s yellow Mercury with body. Fled south onto an unpaved road in next county. Then went west and climbed. Road made of muddled dust; pink-feldspar. Dust was granite, but compared to bedrock was deficient in iron and magnesium. * As he climbed further, came into Pike’s Peak granite – very distinctive. * *At 7200 ft, Osborne dumped body in dump used by an Ashram. Body would not be found for 7 months. *Osborne went east and went on an unpaved road of black slags and drifted sands on a New Jersey barrier island. He hid car and torched it with gasoline. * *FBI investigation turned up Osborne in New Jersey *Although Osborne (discovered to be Joseph Corbett, Jr) covered his tracks well but was writing his itinerary on the bottom of his car. *4 depositional strata found: * 4th contained material from around New Jersey dump where he burned car * 3rd contained pink feldspars of Pike’s Peak granite – near where body was found * 2nd had materials from Morrison hogback formation – around Coor’s ranch * 1st had pink feldspars of other Front Range granites – generally related to Rocky Mountain Front Range * * Story of how FBI geologist, Ron Rawalt was able to determine, with certainty, where Camarena body was buried, thus showing that Mexican govt. lied about how he was killed. * He noticed a TV report of the killings. The body was shown with soil clinging to it. The soil was obviously of a different color than the soil from the alleged burial site. * * He told the govt. that he could prove, with soil analysis alone, that Mexican govt. was lying about the murder. * He went to Mexico and collected a spoonful of soil from Camarena body. He compared that to the soil from the alleged burial site and found them to be entirely different. * *Soil from body *Spoke of mountains *98% rhyolite ash (clean, high in silica, angular, vesicular) – could be described as “airfall pumice” *Bixbyite – blacker than coal *Pink glass of exceptional depth and richness of color, he had never seen anything like it, except in candy *2 kinds of cristobalite: opalized and clear, elongate and faceted, clear polygonal columns (octehedrons). Resembled branch coral. Very rare to find both types together. * * Pinpointing location * Research with Geological Survey and Smithsonian minerologists located specific location – A Jalisco state park called Bosques de la Primvera. Cristabolite was the result of a third-event calderea formation. * Location is on upslope of mountain in park or park itself * Rawalt flew to Mexico as “DEA agent” (FBI agents were not allowed in to investigate * * While Rawalt was in Mexico searching for the area of burial, FBI was approached about a French consultant, Loic Le Ribault. He was the head petrologist for the French national oil company and was said to be able to do things geologically speaking, that other people couldn’t do. Show him a few grains of sand and he could tell you where they came from * *Le Ribault *FBI tested him by giving him 3 samples: * Ash from Mt. St. Helens * Alluvium from river delta in S. Carolina related to recent murder * Dirt from girders taken from bomb site in Beirut, Lebanon *Ribault’s results: * Got location of ash from Mt. St. Helens within a few miles of source * River basin in American Southest * Bekaa valley in Lebanon – soil had been subjected to explosion * * Le Ribault’s contribution to Camarena case *Was showed samples from park and body. He said “you are there, but not there”. Right elevation, but these are samples (from park) from an area washing north. The site is an area washing south. *Sand deposited by water 4-5 ft. deep in a draw. of draw <10 degrees. Shade predominates. *Rawalt found exact location from this data. * Slope *The value of soil as evidence rests with its prevalence at crime scenes and its transferability between the scene and the criminal. *Most soils can be differentiated by their gross appearance. *A side-by-side visual comparison of the color and texture of soil specimens is easy to perform and provides a sensitive property for distinguishing soils that originate from different locations. * *In many forensic laboratories, forensic geologists will characterize and compare the mineral content of soils. *Some crime laboratories utilize density-gradient tubes to compare soils. *These tubes are typically filled with layers of liquids that have different density values. *When soil is added to the density-gradient tube, its particles will sink to the portion of the tube that has a density of equal value. * *Standard/reference soils are to be collected at various intervals within a 100-yard radius of the crime scene, as well as the site of the crime, for comparison to the questioned soil. *Soil found on the suspect, such as adhering to a shoe or garments, must not be removed. *Instead, each object should be individually wrapped in paper, and transmitted to the laboratory. * * Do Now: What type of chemical are most narcotics? Chapter 5 * Today students will * Understand basic chemical substances * Apply chromatography * Understand separation techniques * *An element is the simplest substance known and provides the building block from which all matter is composed. *Matter is anything that has a mass and occupies space. *All of the elements are listed by name and symbol in the periodic table. *Two or more elements combine to form a compound. *An atom is the basic particle of an element and a molecule is the smallest unit of a compound. * *Matter can be classified according to the physical form it takes. *Solid-definite shape and volume *Liquid-specific volume, takes the shape of its container *Gas/vapor-neither a definite shape nor volume *Substances can change from one phase to another without forming a new chemical species, * matter is simply being changed from physical state to another. *Whenever a situation exists in which a substance can be distinguished by a visible boundary, different phases exist. * *The proper selection of analytical techniques that will allow the forensic scientist to identify or compare matter can best be understood by categorizing all substances into one of two broad groups: 1. 2. organics inorganics. *Organic substances contain the element carbon, commonly in combination with one or more other elements. *Inorganic materials include all other known chemical substances. * *Another consideration in selecting an analytical technique is the need for either a qualitative or a quantitative determination. *Qualitative relates just to the identity of the material, whereas quantitative requires the determination of the percent composition of the components of a mixture. *Most of the evidence received by crime laboratories requires the identification of organic compounds. * * * All of the following are readily used by a forensic scientist to identify or compare organic materials. * Chromatography, * Spectrophotometry * Mass spectrometry * Chromatography is a means of separating and tentatively identifying the components of a mixture. * Spectrophotometry is the study of the absorption of light by chemical substances. * *Chromatography is based on the observation that chemical substances have a tendency to partially escape into the surrounding environment when dissolved in a liquid or when absorbed on a solid surface. *Those materials that have a preference for the moving phase will slowly pull ahead and separate from those substances that prefer to remain in the stationary phase. 83 * Place a single dot of the unknown substance on the filter paper, near the bottom * Place the paper carefully into the test tube with just enough water to keep the bottom wet, but not enough to touch the dot * Allow it to “run” for about 10 minutes * Record your observations * * *In GC, the moving phase is actually a gas called the carrier gas, which flows through a column. *The stationary phase is a thin film of liquid contained within the column. *After a mixture has traversed the length of the column, it will emerge separated into its components. *The written record of this separation is called a chromatogram. 85 * *The time required for a component to emerge from a GC column is known as retention time. *Solid materials may be heated or pryolyzed to high temperatures so that they will decompose into numerous gaseous products to flow through the GC column. 86 * *Other forms of chromatography found to be applicable to forensic science problems are high-performance liquid chromatography (HPLC) and thin-layer chromatography (TLC). *Both chromatographic systems, as with any chromatography, require having a moving phase and a stationary phase. 87 * *HPLC separates compounds using a stationary phase, a column filled with fine solid particles, and a mobile liquid phase. *As the liquid carries the sample through the column, different components are slowed down to different degrees, depending on their interaction with (attraction to) the stationary phase. *The major advantage of HPLC is that the entire process takes place at room temperature. *Substance, such as organic explosives, which are heat sensitive are more readily separated by HPLC. 88 * *TLC uses a solid stationary phase usually coated onto a glass plate and a mobile liquid phase to separate the components of the mixture. *The liquid will slowly rise up the plate by capillary action causing the sample to become distributed between the stationary phase and the moving liquid phase. *Because most compounds are colorless, the materials must be visualized by placing the plates under ultraviolet light or spraying the plate with a chemical reagent. *The distance a spot travels up a thin-layer plate can be assigned a numerical value known as the Rf value. * * A technique analogous to TLC is electrophoresis. *Here, materials are forced to move across a gel-coated plate under the influence of an electrical potential. *In this manner, substances such as proteins and DNA can be separated and characterized. * DO NOW: Explain the principle of chromatography, how does it work? * Today students will * Understand basic properties of light * Interpret light as particle and wave * Apply understanding of light to chemical analysis of substances * * * A technique analogous to TLC is electrophoresis. *Here, materials are forced to move across a gel-coated plate under the influence of an electrical potential. *In this manner, substances such as proteins and DNA can be separated and characterized. * *Two models describe the behavior of light. *Light is described as a continuous wave. *Light is depicted as a stream of discrete energy particles. *When white light passes though a prism, it is dispersed into a continuous spectrum of colors. 94 * Visible light ranges in color from red to violet in the electromagnetic spectrum. * Waves are described in terms such as: * Wavelength, the distance between two successive crests (or one trough to the next trough). * Frequency, the number of crests (or troughs) passing any one given point per unit of time. * * *Frequency and wavelength are inversely proportional to one another. *The electromagnetic spectrum is the entire range of radiation energy from the most energetic cosmic rays to the least energetic radio waves. *Visible light is only a small part of the electromagnetic spectrum. *As electromagnetic radiation moves through space, its behavior can be described as that of a continuous wave; * However, once radiation is absorbed by a substance, it is best described as discrete particles of light known as photons. * *Just as a substance can absorb visible light to produce color, many of the invisible radiations of the electromagnetic spectrum are likewise absorbed. *The quantity of light absorbed at any frequency is directly proportional to the concentration of the absorbing species. This is known as Beer’s Law. * 98 * *Spectrophotometry, an important analytical tool, measures the quantity of radiation that a particular material absorbs as a function of wavelength and frequency. * *The spectrophotometer is the instrument used to measure and record the absorption spectrum of a chemical substance. *The components of a spectrophotometer are: *A radiation source *A monochromator or frequency selector *A sample holder *A detector to convert electromagnetic radiation into an electrical signal *A recorder to produce a record of the signal *Absorption spectra can be done in the visible, ultraviolet (UV) or infrared (IR) regions. 100 * *Most forensic laboratories use UV and IR spectrophotometers to characterize chemical compounds. *The simplicity of the UV spectrum makes it a useful tool for determining a material’s probable identity, although it may not provide a definitive result. 101 *The IR spectrum provides a far more complex pattern. *Different materials always have distinctively different infrared spectra; *each IR spectrum is therefore equivalent to a “fingerprint” of that substance. * * DO NOW: How can the properties of light allow it to be used for chemical analysis? * Today students will: * Finish Applying chemistry concepts to the analysis of organic materials * Compare analysis techniques for precision * Explain the concepts of Inorganic Trace element analysis * List the Six techniques available to forensic scientists for determining the elemental composition of materials * * *In the mass spectrometer, a beam of high-energy electrons collide with a material, producing positively charged ions. *These positive ions almost instantaneously decompose into numerous fragments, which are separated according to their masses. 105 •Under carefully controlled conditions, no two substances produce the same fragmentation pattern. * * *A direct connection between the GC column and the mass spectrometer allows each component to flow into the mass spectrometer as it emerges from the GC. *The separation of a mixture’s components is first accomplished by the GC. *Then, fragmentation of each component by high-energy electrons in the mass spectrometer, will produce a distinct pattern, somewhat like a “fingerprint,” of the substance being examined. 107 * (15 minutes)Work Independently and silently to answer the following questions You may use your own notebook, but no other resources! 1. 2. 3. 4. 5. 6. 7. Explain the basic properties of light Under what conditions does light behave like a particle? Under what conditions does light behave like a wave? How can our understanding of light be used for chemical analysis of substances? How does combining Gas Chromatography and Mass Spectrometry effect the evidence produced from a sample? Which of the analysis techniques result in specific identification of a substance? Which of the analysis techniques result in quantifying of a substance? * * *Inorganic, or non-carbon containing substances, will often be encountered as physical evidence. *Such as tools, coins, weapons, explosives, poisons, and metal scrapings as well as trace components in paints and dyes. *Many manufactured products and most natural materials contain small quantities of elements, known as trace elements: * present in concentrations of less than 1 percent. * *The presence of these trace elements is particularly useful *They provide “invisible” markers that may: *establish the source of a material *or at least provide additional points for comparison. *In each case, the forensic scientist must perform tests that will ultimately determine the specific chemical identity of the questioned material, to the exclusion of all others. * *Six techniques available to forensic scientists for determining the elemental composition of materials are: * Emission spectroscopy * Inductively coupled plasma * Atomic absorption spectrophotometry * Neutron activation analysis * X-ray diffraction * X-ray analyzer (to be discussed in Chapter 7) * 113 *An emission spectrograph vaporizes and heats samples to a high temperature * So the atoms present in the material achieve an “excited” state. *Under these circumstances, the excited atoms will emit light. *If the light is separated into its components, one observes a line spectrum. *Each element present in the spectrum can be identified by its characteristic line frequencies. *Emission spectra can than be matched line for line in a comparison between samples. * *Inductively coupled plasma emission spectrometry (ICP) * the sample, in the form of an aerosol, is introduced into a hot plasma, creating charged particles that emit light of characteristic wavelengths corresponding to the identity of the elements present. *Two areas of forensic casework where ICP has been applied are the identification and characterization of mutilated bullets and glass fragments. * 115 * In atomic absorption spectrophotometry, the specimen is heated to a temperature that is hot enough to vaporize its atoms while leaving a substantial number of atoms in an unexcited state. * The vaporized atoms are then exposed to radiation emitted from a light source specific for a particular element. * If the element is present in the material under investigation, a portion of the light will be absorbed by the substance. * The concentration of the absorbing element will be directly proportional to the quantity of the light absorbed and many elements can now be detected at levels that approach one-trillionth of a gram. * 116 *An atom is composed of a nucleus containing protons and neutrons, with electrons found outside the nucleus in electron orbitals. *The orbitals are associated with a definite amount of energy called an energy level. * 117 * Each element has its own set of characteristic energy levels at varying distances from the nucleus. * Because energy levels have fixed values, an atom will absorb only a definite value of energy, which may come from heat or light. * This absorbed energy pushes the electrons into higher energy level orbitals and the atom is now considered in an excited state. * *Atomic absorption spectrophotometry measures the amount of light energy absorbed by an atom when exciting electrons. *Normally, the electrons will not stay in this excited state for long, and they will quickly fall back to their original energy level, releasing energy in the form of light emission. *Emission spectroscopy collects and measures the various light energies given off by the atom. *The specific frequency of light absorbed or emitted can be determined by the relationship E=hf, where E is the energy difference between two orbitals, h is a universal constant called Planck’s constant, and f is frequency. *Because each element has its own characteristic set of energy levels, each will emit a unique set of frequencies. * 119 * Observe the emission spectra (5 min) * Record your observations * * Working in pairs: (15 min) * Read the given article and determine which type of analysis was needed to evaluate the evidence from the 1963 assassination * Determine if you believe the correct person was arrested * Prepare to share out * * Do Now: What evidence was extensively study in the Kennedy assassination case? *Today students will: *Explain the concepts of Inorganic Trace element analysis *Understand the processes of Neutron Activation and x-ray diffraction. *Analyze the case of “Death by Radiation Poisoning” * * Which type of analysis was needed to evaluate the evidence from the 1963 assassination? * Does the evidence show that the correct person was arrested? * * Made up of: * Protons (+) * Neutrons (0) * Atomic number: refers to the number of protons * Is different for every atom * Determines the atoms identity * The number of P + the number of N = the atomic mass number * Atoms with the same number of protons can have different numbers of neutrons (O can have atomic mass of 15 or 16) * Isotopes are atoms of the same element which have different numbers of neutrons therefore have different mass numbers * Nuclear notation indicates the atomic number and the mass number of isotopic elements * *Radioactivity is the spontaneous emission of radiation by an unstable atomic nucleus. *Radioactive decay is the release of radiation by radioactive isotopes. *The three types of decay are: *Alpha *Beta *Gamma decay * *Alpha decay is the release of alpha particles (2 protons and 2 neutrons). *Alpha particles are represented as or α. •Alpha particles, which are large in size, collide with objects around them. *Do not penetrate very deeply *Are easily stopped by a thin layer of material. * Parent Daughter alpha particle The parent element turns into a daughter element * Two protons and neutrons are lost The protons and neutrons leave as an alpha particle. + Energy! * Beta decay is the release of beta particles from a decaying nucleus. *A beta particle is a high energy electron with a 1charge. *Beta particles are written as β- or *Beta particles pass more easily through matter than alpha particles and require sheets of metal, blocks of wood or specialized clothing to be stopped. * * •A neutron becomes a proton (which stays in the nucleus) and electron (which is ejected from the atom). •ADD A PROTON and LOSE an ELECTRON + ENERGY *Gamma decay is the release of gamma rays from a nucleus. *A gamma ray is a high energy form of electromagnetic radiation with out a change in mass or charge. * *Gamma rays have high penetrating ability and are very dangerous to living cells. *To stop gamma rays thick blocks of lead or concrete are needed. * * *When gamma decay is expressed in an equation it is expressed as γ. *Electron from beta decay is captured to cause gamma particle to emit. * The following equation shows both gamma and alpha decay occurring. * Decay Type Alpha Beta Gamma Gives off Changes Nuclear notation by: Radiation penetration and harm to cells Alpha Decay Type * Gives off Changes Nuclear notation by: Radiation penetration and harm to cells 2 protons & 2 neutrons= Alpha particle= •Mass number decreases by 4 •Atomic number decreases by 2 •Large particle, easily stopped by cloth •Very low risk Atomic number increases by 1 The mass number stays the same •These high energy particles pass more easily through matter •Need metal sheets to stop •Moderate risk to cells 4 2 He Gamma Beta Beta particle = electron = e 0 -1 A gamma ray a •No change in mass high energy or atomic number form of •BUT does not occur electroalone magnetic •Accompanied by radiation alpha or beta. •Gamma rays have high penetrating ability •To stop gamma rays thick blocks of lead or concrete are needed. • Very dangerous to living cells. *Radiation can be detected with Geiger counters and scintillation counters. *Geiger counters detect ionizing radiation. *Scintillation counters register the intensity of radiation by detecting light. * *Half-life is a term used to describe the time it takes for half of a given amount of a radioactive isotope to decay. *Half-life varies greatly depending on the isotope *However, Each Isotope decays at a particular rate * * Uranium-238 (t½ = 4.5 billion years) *Nuclear chemistry provides a new tool for identifying and quantitating the elements. *A nuclear reactor is simply a source of neutrons that can be used for bombarding atoms * This bombardment causes some neutrons to be captured to produce radioactive isotopes. *To identify the radioactive isotope, it is necessary to measure the energy of the gamma rays emitted as radioactivity. * 141 (15 min) *Read the brief case study *Identify the detection techniques used in this case *What was the method of death *Prepare to Discuss * Analyze the case of “Death by Radiation Poisoning” * Do Now: ? * Today students will * * Decay Type Alpha Beta Gamma Gives off Changes Nuclear notation by: Radiation penetration and harm to cells Alpha Decay Type * Gives off Changes Nuclear notation by: Radiation penetration and harm to cells 2 protons & 2 neutrons= Alpha particle= •Mass number decreases by 4 •Atomic number decreases by 2 •Large particle, easily stopped by cloth •Very low risk Atomic number increases by 1 The mass number stays the same •These high energy particles pass more easily through matter •Need metal sheets to stop •Moderate risk to cells 4 2 He Gamma Beta Beta particle = electron = e 0 -1 A gamma ray a •No change in mass high energy or atomic number form of •BUT does not occur electroalone magnetic •Accompanied by radiation alpha or beta. •Gamma rays have high penetrating ability •To stop gamma rays thick blocks of lead or concrete are needed. • Very dangerous to living cells. *Neutron activation analysis *measures the gamma-ray frequencies of specimens that have been bombarded with neutrons. *provides a highly sensitive and nondestructive analysis for simultaneously identifying and quantitating 20 to 30 trace elements. *neutron activation analysis has been used on find trace elements in metals, drugs, paint, soil, gunpowder residue, and hair. *Because this technique requires access to a nuclear reactor, it has limited value to forensic analysis. * 147 *X-ray diffraction is applied to the study of solid, crystalline materials. *As the X-rays penetrate the crystal, a portion of the beam is reflected by each of the atomic planes. *As the reflected beams leave the crystal’s planes, they combine with one another to form a series of light and dark bands known as a diffraction pattern. *Every compound is known to produce its own unique diffraction pattern, thus giving analysts a means for “fingerprinting” inorganic compounds. * 148