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Forensic Determination of Metals
4/5/12
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Encounters with metals
Bomb investigations Counterfeit detection Structural analysis Motor oils Trace evidence
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Identifying a metal Various methods Magnetism- iron based
Instrumentation - ICP: Induction Coupled Plasma X-ray backscatter Chemical reactivity ReDox analysis Hardness, malleability Density Specific heat capacity
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Magnetic metals Most alloys of iron - especially Fe + Ni or Fe + Co
Non magnetic - aluminum, brass, copper, zinc.
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Induction couple plasma
High frequency electromagnetic plasma torch excites metal electrons. Allows atomic emission spectrum to be generated. Spectrum analysed and compared to known standards. Very sensitive and quantitating
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X-ray backscatter Part of a scanning electron microscope. Measures energies of X-rays derived from reflected electrons. Metals have characteristic energies of electrons they can absorb. The reflected ones will bounce off and can be detected by the x-rays They emit when they hit a heavy metal target.
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Backscatter electron detector
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SEM Electron/Specimen Interactions Incident Beam - composition info
When the electron beam strikes a sample, both photon and electron signals are emitted. Incident Beam Backscattered electrons X-rays - composition info - Atomic number and topographical Cathodoluminescence - Electrical Secondary electrons Auger electrons - Surface sensitive compositional - Topographical Specimen Specimen Current Electrical
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Chemical Reactivity Metals like to lose electrons
Aluminum is the only metal that will react with base (NaOH) All other metals will react with acid -Copper turns blue with nitric acid (HNO3) -Magnesium and zinc turn nitric acid hot and yellow -Lead will make an orange gel if mixed with equal parts nitric and acetic acid. -The rates of reaction can be used to distinguish metals. -In HCL, Mg is very reactive, but nickel is less so, and Fe even less
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Hardness + Malleability
Pb is soft and malleable arranged from high to low malleability are silver, lead, copper, aluminium, tin, platinum, zinc, iron and nickel Hardness (sclerometer) Pb (1), Tin (2.5) , Zn (6) , Cu (8) Fe (15) Steel (21) Cast iron (36), Ni (31) , Vn steel (35)
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Density D = Mass/volume Al 2712 kg/m3 Brass 8430 Fe 7850 Pb 11340
Zn Ni Mg Sn
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Specific Heat Capacity
The ability to hold heat without increasing in temperature Metal (kJ/kg K) Al Fe Pb Mg Sn Ti Zn Ag
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Calculating SH Q = mCDT Q = heat energy m = mass C = specific heat DT = change in temp Heat metal to a known temperature, drop into water of known temperature, measure change. Set equations equal to each other - solve SH water kj/kg K
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redox Zn + 2HCl -> Zn2+ + H2 +2Cl- Lose electrons = oxidation
Gain electrons = Reduction Tendency to gain or lose electrons related to Electronegativity, but can also be predicted by Known reduction potentials
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Making a battery to test reduction potential
Cathode (Reduction) Half-Reaction Standard Potential E° (volts) Li+(aq) + e- -> Li(s) -3.04 K+(aq) + e- -> K(s) -2.92 Ca2+(aq) + 2e- -> Ca(s) -2.76 Na+(aq) + e- -> Na(s) -2.71 Zn2+(aq) + 2e- -> Zn(s) -0.76 Cu2+(aq) + 2e- -> Cu(s) 0.34 O3(g) + 2H+(aq) + 2e- -> O2(g) + H2O(l) 2.07 F2(g) + 2e- -> 2F-(aq) 2.87 Zn + CuCl2 Cu + ZnCl2 = 1.1 volts Use a known metal electrode, and acid to generate metal salt, Measure potential.
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On the cathode, reduction takes place.
Oxidant + n e- ® Reductant Example: Cu e ® Cu Cu2+ is the oxidizing agent and Cu the reducing agent. On the anode, oxidation takes place. Reductant ® n e- + Oxidant Example: Zn ® Zn e-. Zn is the reducing agent, and Zn2+ the oxidizing agent.
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Ni(s) + 2 Fe3+ Ni2+ + 2 Fe2+ .77 + .25 = 1.02 volts
Oxidation takes place at the anode, and the electrode must be Ni | Ni2+, Ni(s) Ni2+(aq) + 2 e and the reduction occurs at the cathode: Fe3+, Fe2+: 2 Fe e 2 Fe = volts
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Analysis of Metal Particles A Qualitative Analysis Approach
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