1/25/16 ANNOUNCEMENTS SELECTING AN ANALYTICAL METHOD

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1 1/25/16 ANNOUNCEMENTS SELECTING AN ANALYTICAL METHOD 1

2 TYPES OF ERRORS IN THE LABORATORY 1. Random error Always present, all direchons OJen limits precision of measurements QuanHfy: standard deviahon 2. Systema1c Affects all measurements in the same way- DirecHon and magnitude Assignable cause QuanHfy: bias Error Family Tree 3. Gross Big oops! Generally clear Outliers? SOURCES OF EXPERIMENTAL NOISE Chemical Experiments are affected by uncontrollable environmental condihons affechng system Instrumental noise Affects all components of the instrument Observed noise is a complex composite of all noise sources 2

3 SOURCES OF INSTRUMENTAL NOISE 1. Thermal/ Johnson 2. Shot noise 3. Flicker noise 4. Environmental noise IMPROVING S/N STATISTICS 3

4 LIGHT- MATTER INTERACTIONS CHEM 314 OBJECTIVES Review electromagnehc radiahon and EM spectrum Wave-parHcle duality Overview of ways light can interact with maaer Apply these interachons to the study of chemical systems Summarize excitahon and relaxahon within an atom or molecule using a Jablonski diagram. 4

5 Spectroscopy? InteracHon between light and maaer ELECTROMAGNETIC RADIATION A amplitude p period (sec) ν Frequency (sec -1 ; Hz) λ Wavelength (m- nm) v velocity of propagahon wave number (1/λ; cm -1 ) P power (energy s -1 ) I intensity (P solid angle -1 ) 5

6 WAVELENGTH, FREQUENCY, AND ENERGY What is the frequency and energy of 500nm light? WAVELENGTH, FREQUENCY, AND ENERGY 6

7 ELECTROMAGNETIC SPECTRUM Wavenumber (cm -1 ) Frequency (Hz) Wavelength (m) INTERACTIONS BETWEEN LIGHT AND MATTER λ ν 89.9 x10 6 Hz Public Radio Molecular Molecular rotahons vibrahons Electronic transihons Core electron Nuclear ejected transihons 7

8 INTERACTIONS BETWEEN LIGHT AND MATTER 8

9 SUPERPOSITION OF WAVES INTERACTIONS BETWEEN LIGHT AND MATTER LIGHT AS A WAVE DiffracHon RefracHon Transmission ReflecHon Scaaering PolarizaHon LIGHT AS A PARTICLE Photoelectric effect AbsorpHon Emission Scaaering 9

10 DIFFRACTION- BENDING OF LIGHT AS IT PASSED THROUGH A SLIT Wave generator Wave generator YOUNG EXPERIMENT (1800)- PROVED LIGHT IS A WAVE 10

11 TRANSMISSION- TEMPORARY POLARIZATION OF MOLECULES RefracHve index: At a given frequency i: n i refrachve index v i velocity of propagahon c speed of light in a vacuum 11

12 DISPERSION- CHANGE IN REFRACTIVE INDEX WITH FREQUENCY Good for lenses Good for prisms REFRACTION- BENDING OF LIGHT AT INTERFACES OF MEDIA Snell s law Less dense Light bends toward normal More dense 12

13 REFLECTION- REFLECTION OF LIGHT AT AN INTERFACE hap://maxgrace.wordpress.com/2010/07/14/the-love-chapter-one-more-hme/ SCATTERING- CHANGE IN MOMENTUM OF EM RADIATION Rayleigh- elashc scaaering Mie- large parhcles Raman- inelashc scaaering 13

14 POLARIZATION- SELECTION OF A SPECIFIC ORIENTATION OF EM RAD. INTERACTIONS BETWEEN LIGHT AND MATTER LIGHT AS A WAVE DiffracHon RefracHon Transmission ReflecHon Scaaering PolarizaHon LIGHT AS A PARTICLE Photoelectric effect AbsorpHon Emission Scaaering 14

15 PHOTOELECTRIC EFFECT 1. Light incident on the photocathode 2. Electrons liberated 3. Voltage at anode adjusted to stop current 4. Stopping voltage depends on cathode substrate and radiahon energy PHOTOELECTRIC EFFECT 15

16 ABSORPTION ABSORPTION Compare atomic and molecular absorphon? Why does atomic absorphon occur at discrete wavelengths while molecular absorphon occur in broad peaks? 16

17 EMISSION 17

18 LUMINESCENCE JABLONSKI DIAGRAM 18

19 JABLONSKI DIAGRAM TRANSITIONS Electronic excita1on- promo1on of an electron to an excited state (electronic, vibra1onal, rota1onal). S 0 à S 1 Nonradia1ve decay (vibra1onal relaxa1on)- vibra1onal energy transferred to other molecules through collisions. Very fast. Excited state à S 1 ground vibra1onal state Fluorescence- emission of photon to return to S 0. S 1 às 0 +hν Internal conversion- radia1onless transi1on to an extremely vibra1onally excited state of S 0 without a change in energy. S 1 às 0 Intersystem crossing- radia1onless transi1on from S 1 to T 1 with no change in energy. Change of electron spin. S 1 àt 1 Phosphorescence- emission of photon to return to S 0. T 1 às 0 +hν JABLONSKI DIAGRAM 19

20 SCATTERING TIMESCALES OF THE FOLLOWING TRANSITIONS. BASED ON THESE OBSERVATIONS, CAN YOU PREDICT WHICH TRANSITIONS MIGHT BE MORE LIKELY TO OCCUR (AND THUS MORE COMMON)? Phenomena Transmission NonradiaHve decay Electronic transihons fluorescence phosphorescence Time scale s s 10-8 s 10-5 s 10-5 to 100 s s 20

21 LOOKING AHEAD Tuesday (Jan 26)- Project Overview (Due Feb 15) Last day for Standard Addi1on (Due Feb 1) Thursday (Jan 28)- Beer s Law (Ch 13, look through deriva1on on website) First day of Consumer Characteriza1on Project Experiment 1: Metals Analysis Due: Prelab 1, Experiment 1 21

22 22

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