Introduction to Spectroscopic Methods , nm

Spectroscopy , nm Color Complementa

 Interaction of radiation and matter Violet 400-420 ry Color
 powerful tool for qualitative and quantitative analysis 400-435 Violet Yellow-green
 include studies with other types of electromagnetic radiation (emr) such as x-ray, Indigo 420-440 435-480 Blue Yellow
ultraviolet, infrared, microwave, and radiofrequency radiation Blue 440-490 480-490 Blue-green Orange
 include techniques that do not involve emr (acoustic, mass, and electron spectroscopy) 490-500 Green-blue Red
 widely used tools for the elucidation of the structure of molecular species as well as the Green 490-570 500-560 Green Purple
qualitative and quantitative determination of both inorganic and organic compounds 560-580 Yellow-green Violet
Electromagnetic radiation (emr) Yellow 570-585
580-595 Yellow Blue
 Form of energy transmitted through space at enormous velocities Orange 585-620 595-650 Orange Blue-green
 Can be treated as discrete packets of energy or particles (photon or quanta)
650-750 Red Green-blue
 Has both particle and wave properties Red 620-780

Why is an aqueous solution of Fe(SCN)2+ red?

Because the complex absorbs the green component from the incoming radiation and transmits the
red component
Type Wavelength Interaction
 Consists of particles called photons Gamma –4 Nuclear Emission
5 x 10 - 0.14 nm
E = hν = hc/λ = hcν
X-ray –2 Atomic ionization
h = Planck’s constant = 6.63 x 10 – 34 J-s 10 - 10 nm
ν = frequency ( s – 1 or Hz) UV 10 – 380 nm Electronic transitions
c = speed of light = 3.00 x 10 8 m/s
Vis 380 – 780 nm Electronic transitions
λ = wavelength (μm or nm or Å)
ν = wavenumber (cm– ) IR 780 – 100, 000 nm Bond interaction
As λ increases, ν decreases, E of the photon decreases Radio meters Nuclear absorption
1. Calculate the wavenumber of a beam of infrared radiation with a wavelength of 5.00 μm.

Absorption of Radiation
2. Calculate the energy in joules of one photon of radiation with a wavelength of 8.00 μm.
ABSORPTION
- A process in which a chemical species in a transparent medium selectively attenuates
(decreases the intensity of) certain frequencies of electromagnetic radiation
The Electromagnetic Spectrum b
• Encompasses an enormous range of wavelengths and frequencies (and thus energies)
• Depicts qualitatively the major spectral regions Po = incident radiation
P = transmitted radiation po
• Divisions are based upon the methods required to generate and detect the various kinds of P
radiation b = path length in cm
Optical methods Absorbing solution of
- spectroscopic methods based upon ultraviolet, visible, and infrared radiation concentration c
 Quantitative Measures of Beam Attenuation For monochromatic radiation, absorbance is directly proportional to the path length b
• Transmittance, T through the medium and the concentration c of the absorbing species.
T = P/Po A = abc A = Absorbance
% T = (P/Po) x 100 A = εbc a = absorptivity
• Absorbance, A b = pathlength in cm
A = - log T = log (Po/P) If c is in g/L, a is in L/g-cm c = concentration
If c is in mol/L, Ɛ is in L/mol-cm ε = molar absorptivity

Application of Beer’s Law to Mixtures

Atotal = A1 + A2 + … + An
Atotal = ε1bc1 + ε2bc2 + … + εnbcn

Exercises
1. A solution containing 4.48 ppm KMnO 4 has a transmittance of 0.309 in a 1.00-cm at 520
nm. Calculate the molar absorptivity of KMnO4.

2. A solution containing the complex formed between Bi(III) and thiourea has a molar
absorptivity of 9.32 x 103 L - cm – 1 - mol – 1 at 470 nm.
1. Express the following absorbances in terms of percent transmittance: a. What is the absorbance of a 6.24 x 10 – 5 M solution of the complex at 470 nm in a 1.00-
a. 0.064 b. 0.765 c. 0.318 cm cell?
b. What is the percent transmittance of the solution described in (a)?
c. What is the molar concentration of the complex in a solution that has the absorbance
described in (a) when measured at 470 nm in a 5.00-cm cell?
2. Convert the following transmittance data to absorbances:
a. 19.4% b. 0.863 c. 27.2%

Atomic Absorption
When a beam of polychromatic ultraviolet or visible radiation passes through a medium
containing gaseous atoms, only a few frequencies are attenuated by absorption, and the spectrum
consists of a number of very narrow (0.005 nm) absorption lines

Molecular Absorption
Molecular absorption in the ultraviolet and visible regions consists of absorption bands
made up of closely spaced lines. The typical absorption band consists of a multitude of lines.
In a solution the absorbing species are surrounded by solvent, and the band nature of molecular
absorption often becomes blurred because collisions tend to spread the energies of the quantum
states, thus giving smooth and continuous absorption peaks.
 3. The equilibrium constant for the conjugate acid/base pairHIn + H2O  H3O+ + In –
Limitation to Beer’s Law
is 8.00 x 10 – 5. From the additional information below 1. Real Limitations
Species Absorption Molar Absorptivity - encountered only in relatively concentrated solutions;
Maximum, nm Calculate the absorbance at 430 nm refractive index may change with concentration, hence changing
430 nm 600 nm and at 600 nm in a 1.00-cm cell molar absorptivity
HIn 430 8.04 x 10 3 1.23 x 10 3 when the indicator concentration is At high concentrations (usually > 0.01M), the average
In –
600 7.75 x 10 2 6.96 x 10 3 3.00 x 10 – 4 M. distance between the species responsible for absorption is
diminished to the point where each affects the charge
distribution of its neighbors, hence, their ability to absorb a
given wavelength of radiation is altered.
2. Apparent chemical deviation
- arises when an analyte dissociates, associates, or reacts with a
solvent to generate a product that has a different absorption
spectrum from that of the analyte
Ex. HIn  H+ + In –
color 1 color 2
–
Positive deviation at 430 nm due to absorbance of In
Seatwork: Negative deviation at 570 nm due to absorbance of HIn
The molar absorptivities of the weak acid, HIn (Ka = 1.42 x 10 – 5), and its conjugate base, In –, at
430 nm and 570 nm were determined by measurements of strongly acidic and strongly basic
solutions of the indicator (where essentially all of the indicator was in the HIn and In – form, 3. Apparent instrumental deviations with polychromatic radiation
respectively. The results were
Ɛ430 Ɛ570 - law is adhered only with truly monochromatic
HIn 6.30 x 10 2 7.12 x 10 3 radiation
– 4
In 2.06 x 10 9.61 x 10 2 - In practice, devices can only
Calculate the absorbance at 430 nm and at 570 nm when the indicator concentration is 4.00 x 10 – 5. have a band of wavelengths
around the desired one
- Measurements are done at λmax
where Beer’s law is followed
 1. Measuring the potential under static conditions of no current flow.
2. Measuring the potential while controlling the current.
3. Measuring the current while controlling the potential
4. Instrumental deviations in the presence of All designs above are based on Ohm’s Law:
stray radiation A current, i, passing through an electric circuit of resistance, R, generates a potential, E
- absorbance measurements is usually E = iR
contaminated with small amounts of stray POTENTIOMETRY
radiation, Ps, (result of scattering  Involves measurement of potential under conditions where current is zero
phenomena off the surfaces of prisms,  Measured potential is related to concentration of analyte of interest thru Nernst Equation
lenses, filters, and windows) due to instrumental  Used for locating end points in titrations
imperfections  Equipment:
The observed absorbance is given by - simple and inexpensive
A’ = log [(Po + Ps) / (P + Ps) ] - include reference electrode, indicator
ELECTROANALYTICAL METHODS electrode and potential-measuring device (voltmeter)
-Measurement of potential, current or charge serves as the analytical signal
Bulk methods
-Measure properties of whole solution
Interfacial methods
-The signal is a function of phenomena occurring at the interface between an
electrode and the solution in contact with the electrode Ecell = Eind – Eref + Ej
Interfacial electrochemical methods Reference electrode
Static Methods – no current passes between the electrodes ; concentration of species in the - has accurately known electrode potential
- potential is independent of concentration of analyte/any other ions in solution under study
electrochemical cell is unchanged
Indicator Electrode
Dynamic Methods – current flows and concentrations change as a result of redox reaction - immersed in solution of analyte
Electrochemical cell - develops potential that depends on the activity of the analyte
Consist of two electrodes:
Working or indicator electrode Junction potential
- potential of this electrode is sensitive to analyte’s concentration
Counter electrode
- serves to complete electric circuit
- provides reference potential against which working electrode’s potential is measured
- potential ideally remains constant so any change in overall potential is attributed to
working electrode
In dynamic methods…
 Passage of current changes concentration of species
 Potential of counter electrode may change over time
 Problem is eliminated by replacing counter electrode with two electodes:
 Reference electrode – no current flows; potential remains constant
 Auxiliary electrode – completes the circuit; current is allowed to flow

Experimental designs of electrochemical cells

 [Cl-] does not change if some liquid evaporates
A potential (voltage difference) that develops at the interface
of two solutions of different composition
-Usually a few millivolts or less (sometimes negligible)
Silver-silver Chloride
Reference Electrode
Ag electrode
immersed in a solution of KCl
that has been saturated with
AgCl

-Minimized by placing salt bridge between the two solutions

Ag / AgCl(sat’d), KCl
-Salt bridge is most effective if mobilities of ions are nearly
equal and of large concentrations (sat’d) // E = 0.917 V
 Saturated KCl AgCl(s) + e- 
A 0.1M NaCl solution was placed in contact with 0.1M Ag(s) + Cl- (aq)
NaNO3 solution. Which side of the junction is positive?
Advantage:
-Which side of the 0.05M NaCl / 0.05M LiCl junction will be Can be used at temperatures > 60ºC
positive?

standard hydrogen electrode (SHE)

-is difficult to use (requires H2 and a freshly prepared Pt surface)

INDICATOR ELECTRODES
Ideal:
rapid and reproducible response to changes in concentration of analyte ion or group of analyte ions
Reference electrodes Types:
Metallic Electrodes
Calomel Reference Electrode Membrane Indicator Electrodes
-consists of Hg in contact with a saturated solution of Hg 2Cl2 (calomel) and contains KCl Ion-sensitive Field Effect Transistors
of known concentration
Hg / Hg2Cl2(sat’d), KCl (xM) // METALLIC INDICATOR ELECTRODES
Hg2Cl2(s) + 2 e-  2 Hg(l) + 2 Cl- (aq) Electrodes of the first kind
Advantage:  Pure metal electrode in direct equilibrium with its cation in the solution
Hg22+ ions react with fewer sample components thus clogging at the junction between electrode and  Involves single reaction
analyte solution is minimized  Examples:
Ag+(aq) + e –  Ag(s)
Saturated Calomel Electrode (S.C.E.) Cu2+(aq) + 2 e –  Cu(s)
 Not widely used for potentiometric determinations
E = 0.241 V
Advantage of using saturated KCl: Limitations of Electrodes of the first kind
  Not very selective (also responds to more easily reduced cations)
 Many metals can only be used in neutral or basic solutions (Ex. Zn & Cd dissolve in acidic
solutions)
 Some metals are easily oxidized (can be used only in deaerated solutions)
 Certain harder metals (Fe, Cr, Co, Ni) do not provide reproducible ptentials
 Electrodes used in potentiometry:
Ag/Ag+ , Hg/Hg2+ in neutral solution
Cu/Cu2+, Zn/Zn2+, Cd/Cd2+, Bi/Bi3+, Tl/Tl+, Pb/Pb2+ in deaerated solutions
Metallic redox indicators
 Inert electrodes that serve as source or sink for electrons for redox half reaction
 The potential generally responds to concentration of more than one ion
Use of Ag and S.C.E. to measure [Ag+]  Has limited usefulness for direct potentiometry
Indicator Electrode of the first kind  Example: Pt, Au, Pd, C
+ – Membrane indicator electrodes
Ag (aq) + e  Ag(s) Eº = 0.799V
 Involve measurement of potential that develops across a thin glass membrane that
separates two solutions with different hydrogen ion concentrations
 Also called ion-selective electrodes or p-ion electrodes Combination probe
Glass electrode consisting
(indicator) andofS.C.E.
indicator
Saturated Calomel Reference Electrode  Possess high degree of selectivity for the analyte (respond selectively toand
oneAg/AgCl
ion)
glass
(reference)
electrode
immersed in a solution
reference
of
Hg2Cl2(s) + 2 e-  2Hg(l) + 2Cl- (aq) Eº = 0.241V  A thin membrane capable of binding only the intended ion electrode
unknown pH electrode
Gghjuuknnnnnnn,gunn 
Allows
rapid

determination of several cations and anions by direct potentiometry

Classification of membrane indicator electrode

Glass pH Electrode

Electrodes of the second kind

 Metals not only serve as indicator electrodes for their own cations but also respond to the
activities of anion that form sparingly soluble precipitates or stable complexes with such
cations

 Example:
  Consists of a glass indicator electrode and a saturated calomel reference electrode  Membrane surfaces must be hydrated before a glass electrode will function as a pH
immersed in the solution whose pH is sought
Crystalline Membrane Electrode
 Solid membranes that are selective toward anions in the same way that some glasses
respond to cations
Example:
Fluoride ion selective electrode using LaF3

The Glass pH electrode electrode

Most common ion-selective electrode

Errors in pH measurements
Standards
 pH measurements cannot be more accurate than the standards (typically ± 0.01 pH unit)
Junction potential
 Exists at the porous plug near the bottom of the electrode
 If ionic component of analyte solution is different from that of the standard buffer the
junction potential will change even if the pH of the two solutions is the same
 Uncertainty: ± 0.01 pH unit
Junction potential drift
 Compensated by recalibrating the electrode every 2 hours
Alkaline error
 When [H+] is very low and [Na+] is high, the electrode responds to Na+ and the apparent
pH is lower than the true pH

The Hydration Process

Acid error
 in strong acid (pH<0.5), measured pH is higher than actual pH
 Glass is saturated with H+ and cannot be further protonated
Hydration of glass
 A dry electrode requires several hours of soaking before it responds to H + correctly
Temperature
 pH meter should be calibrated at the same temperature at which measurement will be made
Cleaning
 If electrode has been exposed to hydrophobic liquid (ex. oil), it will be cleaned with
solvent that will dissolve the liquid and then conditioned with aqueous solution
 Improperly cleaned electrode may drift the readings for hours while electrode re-
equilibrates with aqueous solution
Optical Materials

•
The cells,
POTENTIOMETRY (Applications)
windows, and
 Measurement of pH of consumer products wavelength-
 Determination of blood gases as important indicators of disease states (clinical lab) dispersing elements in a spectrophotometer or photometer must be transparent in the
 Continuous monitoring of industrial and municipal effluents to determine pH and wavelength region being employed for analyses.
concentration of pollutants
 Determination of CO2 and other related variables in sea water Light sources
 Determination of thermodynamic equilibrium constant
Continuous sources - made up of radiation of all wavelengths within the spectral region
Line sources -consist of one or more very narrow bands (<0.01 nm) of radiation of known
INSTRUMENTS FOR OPTICAL SPECTROMETRY wavelength
Optical methods Requirements: (absorption and fluorescence)
- spectroscopic methods based upon ultraviolet, visible, and infrared radiation - generate a beam with sufficient power
Types of Optical Spectroscopy - Provide a stable output throughout the measurement
• UV-vis absorption spectroscopy (UV-Vis)
• FT-IR absorption/transmission spectroscopy (FTIR) What are the important properties of a source?
• Atomic absorption spectroscopy (AAS) Brightness Line width Background Stability Lifetime
• Atomic fluorescence spectroscopy (AFS)
• X-ray fluorescence spectroscopy (XFS) Black-body radiation for vis and IR
Instrument Components - a tungsten lamp is an excellent source of black-body radiation
 A stable source of radiant energy - operates at 3000 K
 Wavelength selector - produces λ from 320 to 2500 nm
- permits the isolation of a selected wavelength region For IR:
 Sample container/s - Nernst glower (400-20,000 nm)
 Radiation detector or transducer - nichrome wire (750-20,000 nm)
- converts radiant energy to a measurable signal - Globar (1200-40,000)
 Signal processor and readout Black-body radiation
- a truly continuous radiation produced when solids are heated to incandescence
- very high T is needed to cause a thermally excited source to emit a substantial fraction of its
energy
For UV:
- common are deuterium (D2) and hydrogen (H2) lamps
- electric discharge causes D2 to dissociate and emit UV radiation (160 – 325 nm)
- other good sources are: Xe (250 – 1000 nm)
Hg (280 – 1400 nm)
Wavelength Selectors
In absorption spectrometry, a single wavelength is desired at any given time.
The purpose of a wavelength selector (monochromator or filter) is to allow only a specific
wavelength to reach the detector at any given time. However, a single wavelength cannot be
obtained whatever the source.
The effective bandwith of a wavelength selector is the width of the band of radiation in wavelength
units at half-peak height.

Photometers
Simple instruments that use filters to select wavelength. They can only detect a single
wavelength at a time, have a high throughput energy due to the simple optics (good S/N), and are
inexpensive.
Spectrophotometers
Instruments that contain a monochromator or dispersive element that allow them to scan
various wavelengths. More expensive than photometers and usually have a lower S/N due to the
more complex optics.
Spectrometers
A monochromator equipped with a fixed slit at the focal plane.
Spectrophotometers
A spectrometer equipped with a phototransducer at the exit slit.

MONOCHROMATORS

Polychromatic radiation enters

The light is collimated the first concave mirror
Reflection grating diffracts different wavelengths at different angles
Second concave mirror focuses each wavelength at different point of focal plane
Orientation of the reflection grating directs only one narrow band of wavelengths to exit slit
 Type Wavelength Range, nm
Photon Detectors
Phototubes 150-1000
Photomultiplier Tubes (PMT) 150-1000
Silicon photodiodes 350-1100
Photovoltaic cells 400-5000
Photoconductive cells 1000-50,000
Charge-Transfer Devices (CTD)
Thermal Detectors
Thermocouples 600-20,000
Bolometers 600-20,000
Pneumatic cells 600-40,000
Pyroelectric cells 1000-20,000

Photon Detectors
Based upon the interaction of radiation with a reactive surface to produce electrons
(photoemission) or to promote electrons to energy states in which they can conduct electricity
Filters
(photoconduction)
Filters operate by absorbing all but a restricted band of radiation from Ca continuum source
Phototubes
Interference Filters
• a device that indicates the existence of same physical phenomenon
(UV and Vis radiation)
• rely on optical interference to provide a relatively narrow band of radiation, typically 5 to
Signal Processors and Readout
20 nm.
Signal Processors
• consists of a very thin layer of a transparent dielectric material (frequently CaF 2 or MgF2)
- devises that amplify the electrical signal from the detector
coated on both sides with a film of metal that is thin enough so it transmits approximately
- may alter the signal from ac to dc (or the reverse), change the phase of the signal and
half of the radiation striking it and reflects the other half
filter it
Absorption Filters (Vis)
- may also perform mathematical operations on the signal as differentiation, integration or
• usually consist of a colored glass plate that removes part of the incident radiation by
conversion to a logarithm
absorption to give a band of about 30 to 250 nm.
Readout Devices
• generally less expensive and more rugged than interference filters
- digital meters
- scales of potentiometers
for UV: quartz (won’t block out the light)
- recorders
for vis: glass [l 800nm (red) to l 400 nm (violet)]
- cathode-ray tubes
for IR: NaCl (to or 15384 nm or 650 cm-1)
- monitors of microcomputers
KBr (to 22222 nm or 450 cm-1)
CsI (to 50000 nm or 200 cm-1)

Detectors and Transducers

Detector
• a device that indicates the existence of same physical phenomenon
Transducer
• a special type of detector that converts signals such as light intensity, pH, mass, and
temperature into electrical signals that can be subsequently amplified, manipulated, and
finally converted into numbers that are related to the magnitude of the original signal