Spectroscopy a laboratory method of analyzing matter using electromagnetic radiation

The electromagnetic spectrum

Example of spectroscopy Radiation Scale of  Absorption involves: Example of spectroscopy Gamma rays pm Nuclear reactions   x-rays 0.1 nm Transitions of inner atomic electrons Photoelectron spectroscopy (PES) UV/vis nm Transitions of outer atomic electrons UV-Vis spectroscopy, Atomic Emission Spectroscopy, Colorimetry IR mm Molecular vibrations IR, FTIR, Raman microwave Molecular rotations Rotational spectroscopy Radar, radio waves cm  >>m Oscillation of mobile or free electrons NMR

Some spectroscopic methods Used to elucidate structures of crystals and organic compounds NMR Nuclear Magnetic Resonance Often uses carbon-13 (organic chemistry) Like an “MRI of the molecule” IR Infra-red spectroscopy a type of absorption spectroscopy

Types of motion (vibrations) caused by IR radiation Stretching Symmetrical and assymetrical Scissoring Rocking Wagging Twisting

Different “pieces” of molecules absorb different IR wavelengths

The presence of IR absorption of specific wavelengths indicate that molecular “piece” is present in the molecule

Microwaves cause molecular rotations http://www.radiofrequency.com/rftech.html

Spectroscopy a laboratory method of analyzing matter using electromagnetic radiation

Photoelectron Spectroscopy (PES)

Photoelectron Spectroscopy PES apparatus: iramis.cea.fr

Photoelectron Spectroscopy How it works: Sample is exposed to EM radiation Electrons jump out of sample and go through analyzer http://chemwiki.ucdavis.edu

Image source: Inna M Vishik http://www.stanford.edu/~ivishik/inna_vishik_files/Page452.htm

Kinetic Energy Analyzer X-ray or UV Source Kinetic Energy Analyzer 6.26 0.52 Binding Energy (MJ/mol) 3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+

Energy to remove an electron PES Data for Neon Each peak represents the electrons in a single sublevel in the atom The bigger the peak , the more electrons Electrons generally farther from the nucleus Energy to remove an electron “binding energy” often measured in eV (electron volts) 1 eV = 1.60217657 × 10-19 J Electrons generally closer to the nucleus

Hydrogen vs. Helium The helium peak is farther to the right (higher energy) thus more energy is needed to remove the 1s electrons in helium. They must be held more tightly because there is a higher effective nuclear charge. (Helium has 2 protons pulling on 1s but hydrogen only has 1) The helium peak is twice as tall because there are twice as many electrons in the 1s sublevel

Oxygen (1s22s22p4) 4 electrons in 2p 2 electrons in 2s

Scandium (1s22s22p63s23p64s23d1) *Notice that it takes more energy to remove an electron from 3d than from 4s. This is because as electrons are added to 3d they shield 4s thus it’s easier (takes less energy) to remove 4s electrons compared to 3d electrons.

Transition metals… Remember: when transition metals become cations - it’s the s electrons that are lost first! Fe [Ar] 4s23d6 Fe2+ [Ar] 3d6 Fe3+ [Ar] 3d5 The most weakly held electrons are the first to be lost The “order of filling” is not necessarily the same as the “order of removal”!!

Ex1: Identify the element whose PES data is shown Sodium Why is one peak much Larger than the others? This peak represents 6 electrons in the 2p sublevel The other peaks represent only 1 or 2 electrons In which sublevel are the electrons Represented by peak A? 3s A

Ex1: Identify the element whose PES data is shown Molybdenum Why is one peak much Larger than the others? In which sublevel are the electrons Represented by peak A? Represented by peak B? A B

Example 2: oxygen nitrogen #e- #e- increasing energy → increasing energy → The PES data above shows only the peak for the 1s electrons. Why is the peak for Nitrogen farther to the left? It takes less energy to remove a 1s electron from nitrogen because it has a lower effective nuclear charge (fewer protons) than oxygen

Ex3: Sketch the expected PES spectrum for Aluminum

Colorimetry UV/Vis Spectroscopy

Colorimetry and uv/vis spectroscopy - used to find the concentration of colored solutions Many compounds absorb ultraviolet (UV) or visible (Vis.) light. When dissolved in water, the absorption of some of the frequencies (colors) of light causes them to transmit others, and the solutions are thus colored. For example aqueous Cu2+ solutions often appear blue, because the Cu2+ ion absorbs visible light in the 600 – 650nm range.

Co(II) ion Co2+ solutions often appear red to our eyes, because the Co2+ ion absorbs visible light in the 500 – 510nm range (blue-green to green) The “perceived” color is then red.

The diagram below shows a beam of monochromatic radiation of radiant power P0, directed at a sample solution. Absorption takes place and the beam of radiation leaving the sample has radiant power P.

The amount of radiation absorbed may be measured in a number of ways: Transmittance, T = P / P0 % Transmittance, %T = 100 T Absorbance A = log10 P0 / P A = log10 1 / T A = log10 100 / %T A = 2 - log10 %T

The last equation, A = 2 - log10 %T , is worth remembering because it allows you to easily calculate absorbance from percentage transmittance data. The relationship between absorbance and transmittance is illustrated in the following diagram:

Co(II) ion The relationship between absorbance and transmittance

Choose the wavelength with maximum absorbance when analyzing a solution

Beer’s Law Now let us look at Beer’s law - the equation representing the law is straightforward: A=abc Where A is absorbance (no units, since A = log10 P0 / P ) a is the molar absorbtivity with units of M-1 cm-1 b is the path length of the sample - that is, the path length of the cuvette in which the sample is contained. We will express this measurement in centimeters. c is the concentration of the compound in solution, expressed in M

The reason why we prefer to express the law with this equation is because absorbance is directly proportional to the other parameters, as long as the law is obeyed. (We are not going to deal with deviations from the law.)

Beer’s Law – typical scenario Measure the absorbance of a several samples of a solution of known concentrations Plot A vs concentation (usually molarity) This is called a “calibration curve” Should be linear

3. Measure the absorbance of a solution of the same chemical, but with unknown concentration 4. Using the calibration curve, determine the molarity of the unknown solution

Spectrometry a laboratory method of analyzing matter using electromagnetic radiation.

Mass Spectrometry Determines the relative abundance of the different isotopes of an element Used to determine the average atomic mass of an element

a Mass Spectrograph for Ne

Portions adapted from http://teaching.shu.ac.uk/hwb/chemistry/tutorials/molspec/beers1.htm AP 2003 FRQ #5 Chemistry, Chang, 10th edition http://www.radiofrequency.com/rftech.html APSI 2013 OU presentation; J. Beninga Wikipedia: IR spectroscopy gifs http://wwwchem.csustan.edu/Tutorials/images/cychexol.gif http://orgchem.colorado.edu/Spectroscopy/irtutor/images/etbenzat.gif