Instrumental Methods of Chemical Analysis

CLASSIFICATION OF ANALYTICAL METHODS

Classical vs Instrumental Qualitative instrumental analysis is that measured property that indicates presence of analyte in matrix Quantitative instrumental analysis is that magnitude of measured property that is proportional to concentration of analyte in matrix Species of interest All constituents including analyte. Often need pretreatment - chemical extraction, distillation, separation, precipitation
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INTRODUCTION

CLASSICAL: Qualitative - identification by color, indicators, boiling points,odors Quantitative - mass or volume (e.g. gravimetric, volumetric)

INSTRUMENTAL: Qualitative - chromatography, electrophoresis and identification by measuring physical property (e.g. spectroscopy, electrode potential) Quantitative - measuring property and determining relationship to concentration (e.g. spectrophotometry, mass spectrometry). Often, same instrumental method used for qualitative and quantitative analysis.

TYPES OF INSTRUMENTAL METHODS

PROPERTY Radiation Emission Radiation Absorption EXAMPLE METHOD Emission spectroscopy - fluorescence, phosphorescence, luminescence Absorption spectroscopy spectrophotometry, photometry, nuclear magnetic resonance, electron spin resonance Turbidity, Raman Refractometry, interferometry X-ray, electron Polarimetry, circular dichroism

Radiation Scaterring Radiation Refraction Radiation Diffraction Radiation Rotation

TYPES OF INSTRUMENTAL METHODS

PROPERTY Electrical Potential Electrical Charge Electric Current Electrical Resistance Mass Mass-to-charge Ratio Rate of Reaction Thermal Characteristics Radioactivity EXAMPLE METHOD Potentiometry Coulometry Voltammetry - amperometry, polarography Conductometry Gravimetry Mass spectrometry Stopped flow, flow injection analysis Thermal gravimetry, calorimetry Activation, isotope dilution

Often combined with chromatographic or electrophoretic methods

INSTRUMENTS FOR ANALYSIS

Block diagram for the overall process of instrumental measurement.

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General Properties of Electromagnetic Radiation

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The electromagnetic radiation is looked at as sinusoidal waves which are composed of a combination of two fields. An electric field (which we will use, in this course, to explain absorption and emission of radiation by analytes) magnetic field at right angle to the electric field (which will be used to explain phenomena like nuclear magnetic resonance in the course of special topics in analytical chemistry offered to Chemistry students only).
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The classical wave model

The classical wave model describes electromagnetic radiation as waves that have a wavelength, frequency, velocity, and amplitude. These properties of electromagnetic radiation can explain classical characteristics of electromagnetic radiation like reflection, refraction, diffraction, interference, etc. However, the wave model can not explain the phenomena of absorption and emission of radiation.
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We will only deal with the electric field of the electromagnetic radiation and will thus refer to an electromagnetic wave as an electric field having the shape of a sinusoidal wave. The arrows in the figure below represent few electric vectors while the yellow solid sinusoidal wave is the magnetic field associated with the electric field of the 15 wave.

Wave Properties of Electromagnetic Radiation

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Wave Parameters
1. Wavelength () The wavelength of a wave is the distance between two consecutive maxima or two consecutive minima on the wave. It can also be defined as the distance between two equivalent points on two successive maxima or minima

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2. Amplitude (A) The amplitude of the wave is represented by the length of the electrical vector at a maximum or minimum in the wave. In the figure above, the amplitude is the length of any of the vertical arrows perpendicular to the direction of propagation of the wave.
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3. Frequency The frequency of the wave is directly proportional to the energy of the wave and is defined as the number of wavelengths passing a fixed point in space in one second. 4. Period (p) The period of the wave is the time in seconds required for one wavelength to pass a fixed point in space.
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5. Velocity (v) The velocity of a wave is defined as the multiplication of the frequency times the wavelength. This means: V = The velocity of light in vacuum is greater than its velocity in any other medium
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Since the frequency of the wave is a constant and is a property of the source The decrease in velocity of electromagnetic radiation in media other than vacuum should thus be attributed to a decrease in the wavelength of radiation upon passage through that medium.

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6. Wavenumber () The reciprocal of wavelength in centimeters is called the wavenumber. This is an important property especially in the study of infrared spectroscopy. =k

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Electromagnetic Spectrum
The electromagnetic radiation covers a vast spectrum of frequencies and wavelengths. This includes the very energetic gamma-rays radiation with a wavelength range from 0.005 1.4 Ao to radiowaves in the wavelength range up to meters (exceedingly low energy). However, the region of interest to us in this course is rather a very limited range from 180-780 nm. This limited range covers both ultraviolet and visible radiation.
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Mathematical Description of a Wave

A sine wave can be mathematically represented by the equation: Y = A sin (t + ) Where y is the electric vector at time t, A is the amplitude of the wave, is the angular frequency, and is the phase angle of the wave. The angular frequency is related to the frequency of radiation by the relation: = 2 This makes the wave equation become: Y = A sin (2t + )
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Molecular Energy Levels Molecules can have the following types of energy
Kinetic (due to motion) Electronic (PE and KE of electrons) Vibrational (oscillation of atoms in bonds) Rotational

All except the KE are quantized Emolecule = Erotational + Evibrational + Eelectronic

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Molecular Energy Levels

Excited Electronic State

Rotational Energy Levels

Vibrational Energy Levels

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Ground Electronic State

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Rotational Energy of a Diatomc Molecule

This type of Energy is associated with the overall rotation of the molecules with the atoms considered as fixed point mass

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Vibrational Energy

A molecular vibration occurs when atoms in a molecule are in periodic motion while the molecule as a whole has constant translational and rotational motion. The frequency of the periodic motion is known as a vibration frequency, and the typical frequencies of molecular vibrations range from less than 1012 to approximately 1014 Hz.

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