UV - Visible Spectroscopy in Physical Chemistry

UV –visible spectroscopy in physical chemistry
By: Mahmood Mohammed Ali
 Characterization of nanoparticles by using (Uv –visible spectroscopy)
Ultraviolet and visible spectroscopy is used to qualitatively verify the formation of

metallic nanoparticles, as this is done by measuring the surface plasmon resonance
(SPR) spectrum. Nanoparticles are usually different in size and shape. The molecules
are detected initially by using UV–Visible spectroscopy, which depends on the
concentration of the measured solutions, or the amount of light absorbed by the particles
at different wavelengths. In the case of absorption of nanoparticles, Absorption of
nanoparticles is corresponding to SPR.
SPR is a phenomenon that arises from the oscillation of surface electrons in

nanoparticles of noble metals. This phenomenon means light (photons) drives the
oscillation of the excited surface. conduction electrons of the nanoparticle allowing the
photons that hit the surface of the nanoparticle to transfer their energy to the surrounding
surface electrons; turning them into plasmons. The existence of these plasmons affect
the way light is scattered and absorbed, since we know colour is just a visual
manifestation of reflected (not absorbed) wavelengths, changing how/what wavelengths
are absorbed effectively changes the resulting visible colour.SPR phenomenon produces
a distinctive absorption peak, usually in the ultraviolet and visible regions. SPR
phenomenon made nanoparticles suitable for a large range of applications in the fields
of micro-optical devices, photonic circuits, and drug delivery. By change the structure
of nanomaterials, the frequency at which surface electrons oscillate can be changed .
This phenomenon appears in gold, silver, and copper as shown in Figure )1(
Figure)1( SPR in metal nanoparticles

Figure (2): Absorbance for different concentrations of metal nanoparticle
 Ultraviolet and visible spectroscopy to estimate shapes and sizes of the

nanoparticles
The dependence of the optical properties of metal nanoparticles on particle size and
wavelength were analyzed theoretically using multipole scattering theory, where the
complex refractive index of metal was corrected for the effect of a reduced mean free
path of the conduction electrons in small particles.Methods to calculate the particle
diameter (d) from UV-vis spectra are derived, and analytical relations between the
extinction efficiency (Qext) and d are established, which allow the determination of the
particle concentration.
To compare these theoretical results to experimental data, gold nanoparticles in the size
range of 5 to 100 nm were synthesized and characterized with TEM and UV-vis. It is
shown that the nanoparticles produced can be used to determine both size and
concentration of gold nanoparticles directly from UV-vis spectra. Equations for this
purpose are derived, and the precision of various methods is discussed. The major aim
of this work is to provide a simple and fast method to determine size and concentration
of nanoparticles.
B1 is the inverse of the slope (m) B2 = B0/m where B0 is the intercept

 kinetic study by UV spectrophotometry
Analysis of reaction kinetics is a fundamental chemistry technique that is essential for

understanding how these reactions occur. UV-Vis spectrophotometry is often used for
this analysis, when the change in reactant or products can be monitored by absorbance
at a specific wavelength over time.
In this field, the absorbance of samples was monitored by UV-VIS spectroscopy, while
the concentrations of samples and different pH levels may be adjusted to enable students
to obtain a wide range of reaction kinetic data.
The rate of hydrolysis depends strongly upon the pH-value, buffer composition and ionic
strength. Consequently, the half-life of the reaction can be varied from milliseconds to
several hours by the appropriate selection of these parameters. Thus, this reaction is
suitable for testing conventional UV-VIS as well as stopped-flow spectrophotometers
fiqure (3)
Figure (3) stopped-flow spectrophotometers
Kinetic investigations by spectrophotometric methods require that absorbance values be

measured at timed intervals. It is extremely important to understand what is occurring
during chemical reactions and to be able to determine reaction completion, reaction rates
under different conditions and also whether the reactions are single or multi-step.
Spectrosopic techniques, such as UV-Visible spectrometry, can be deployed to observe
the chemical changes taking place during reactions. in many cases the reaction
timescales are too fast to be performed and observed by the simple manual mixing of the
reactants in a cuvette. The stopped-flow technique is frequently used for rapid kinetics
experiments allowing the reactants to mix effectively and react whilst monitoring the
reaction in a low volume cuvette in the UV-Visible instrument.
The reaction rate constant, kapp, can be estimated with a pseudo-first-order kinetic model.
In addition, the reaction temperature was adjusted to investigate the decomposition
activation energy (Ea), Calculation of activation entropy ΔS ≠, as the ΔG= ΔH – TΔS and
ΔH = Ea – RT (for a reaction in homogeneous liquid medium): we can relate the rate
constant kobs to the activation entropy .
Effect of ionic strength μ on the rate constant of the compounds hydrolysis reaction.
Debye-Huckel-Bronsted relation can show the influence of ionic strength on the rate
constant of an ionic reaction
log k = log k0 + 1.02 zA zB μ1/2. (Where k is the specific rate constant, k0 is the specific
rate constant at zero ionic strength and zA and zB are the charges of ions A and B
respectively).
For simple and uniform reactions the rate laws can be formulated in terms of the
absorbance by means of Eq. (2). This can be carried out explicitly on a 1st order reaction
with k1 as the rate constant the rate law reads
For completed reaction
And if the product does not absorb at wavelength A

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UV –visible spectroscopy in physical chemistry

By: Mahmood Mohammed Ali

 Characterization of nanoparticles by using (Uv –visible spectroscopy)

Ultraviolet and visible spectroscopy is used to qualitatively verify the formation of

SPR is a phenomenon that arises from the oscillation of surface electrons in

Figure)1( SPR in metal nanoparticles

 Ultraviolet and visible spectroscopy to estimate shapes and sizes of the

B1 is the inverse of the slope (m) B2 = B0/m where B0 is the intercept

Analysis of reaction kinetics is a fundamental chemistry technique that is essential for

Figure (3) stopped-flow spectrophotometers

Kinetic investigations by spectrophotometric methods require that absorbance values be

For completed reaction

And if the product does not absorb at wavelength A

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