Professional Documents
Culture Documents
Anfisko I/3
Spectroscopy
Originally, the study of the dispersion of visible light into its
component colors (visible spectrum). Now it means the study of
electromagnetic (EM) and other spectra including mass, electron
and acoustic spectroscopy’s.
Spectroscopy
Awalnya, studi tentang dispersi cahaya tampak menjadi
komponen komponen warna (spektrum tampak). Sekarang, merup
studi tentang elektromagnetik dan spektrum lain meliputi massa,
elektron, dan spektroskopi akustik (yang berkaitan dg suara).
General properties of EM radiation
- Time or Distance
Period (p) – the time required for one cycle to pass a fixed point in space.
(wkt yang dibutuhkan satu siklus u/ melewati sebuah titik dalam ruang)
Frequency (n) – the number of cycles which pass a fixed point in space per second.
(jumlah siklus yang melewati suatu titik tertentu per detik)
= 1/p ( s-1 = Hz ) (putaran perdetik)
Wavelength (l) – The distance between two identical adjacent points in a wave
(usually maxima or minima). (jarak antara 2 titik yang
berdekatan yang identik dalam satu gelombang)
Amplitude (A) – The maximum length of the electric vector in the wave (Maximum
height of a wave).
Wavenumber ( n ) - The number of waves per cm in units of cm-1.
• For EM radiation in vacuum and l is in cm, n = 1/l
• Both power and intensity are related to the square of the amplitude (A2) of
an EM wave.
Hubungan antara Energi, frekuensi
dan panjang gelombang
E = h. ν
ν = c/l
E= h.c/l
E= energi radiasi
h = tetapan planck=6,626 x 10-34 Joule
c = kecepatan cahaya = 2,998 x 10-10 cms-1
l= panjang gelombang
Hitunglah kuantitas-kuantitas berikut untuk suatu radiasi
pada panjang gelombang 380 nm :
a. Panjang gelombang dlm angstrom dan dlm cm
1 nm = 10-7 cm =10oA
380 nm = 3800 0A = 3,8x10-5 cm
b. Bilangan gelombang
1/l = 1/3,8 x 10-5
c. Frekuensi
ν = c/l
d. Energi
E = hc/l
• Types spectroscopic methods based on EM radiation.
Hubungan antara warna dengan panjang gelombang
Panjang Warna yang diserap Warna yang
gelombang diamati/warna
komplementer
400-435 Ungu (lembayung) Hijau kekuningan
450-480 Biru Kuning
480-490 Biru kehijauan Orange
490-500 Hijau kebiruan Merah
500-560 Hijau Merah anggur
560-580 Hijau kekuningan Ungu
580-595 Kuning Biru
595-610 Orange Biru kekuningan
610-750 Merah Hijau kebiruan
QUESTION:
P0 – the power of the radiation beam before it passes through the sample
P – the power of the radiation beam after it passes through the sample medium
containing the analyte.
• There are two terms commonly used with absorption methods to describe the
relationship of P0 and P.
1. Transmittance
2. Absorbance
B. Absorption Methods
1. Transmittance - The fraction of incident radiation transmitted
through the sample medium.
%T = T x 100
• Major limitation – transmittance has a nonlinear relationship with concentration
of analyte in the sample.
I. Measurement of Transmittance and Absorbance
A. Transmittance (T)
P
T and %T T 100
P0
Where: P0 = Power of incident beam
P = Power of emergent beam
Power – Energy (in ergs) of radiation
impinging on a 1 cm2 area of
the detector per second.
• In reality, we do not measure the true P0. We measure PSolvent, the power of
the beam passing through a cell containing solvent only.
So:
PSolution
T
PSolvent
B. Absorption Methods
2. Absorbance - A measurement of the amount of radiant power
absorbed by the sample defined as the negative log
of transmittance.
A = -log10T
C. Beer’s Law
• The amount of radiation absorbed is proportional to the thickness of the
absorbing layer (b), the molecular concentration (c) of the analyte, and the
molecular absorbing coefficient (a) of the species, which is characteristic of
the species at a given wavelength.
A abc
• When concentration (c) is expressed in molarity (mol/L) and thickness or
pathlength (b) is expressed in centimeters, the molecular absorbing coefficient
(a) is called molar extinction coefficient (e) and has units of liters per moles
per centimeter [ L/(mol•cm) ].
A ebc
• For mixtures Beer’s Law is additive.
ATotal A1 A2 A3...... An
or
ATotal e1b1c1 e 2b2c2 e 3b3c3...... e nbncn
• The same effect is observed if the salt concentration in the solvent (or
buffer) is too high.
• Limitations of Beer’s Law
2. Chemical Deviations
• A is linear with respect to concentration (c) except under conditions of
high concentration or when chemical reactions are occurring.
Example:
HIn H In -
Color 1 Color 2
3. Instrument Deviations
a. Effect of Polychromatic Radiation
• Ideally, a monochromator will pass radiation of a single wavelength, but in
reality the monochromator passes a band of radiation. The bandwidth of the
spectrometer will affect the linearity of Beer’s Law.
• e will vary across the bandwidth, so a plot of A vs. c can deviate from
linearity.
• Beer’s Law will be linear when the bandwidth is < 1/10 the width of the
absorption peak at half height.
3. Instrument Deviations
b. Scattered Light
• Scattered light that reaches the detector will increase power reaching the
detector.
• Long pathlength cells cause more scattered light, which causes deviations
from linearity in the relationship between A and b.
• Sample and reference are measured simultaneously and the signal from the
reference is subtracted from the sample signal.
c. Xe lamp
• Used when a high intensity lamp is required and emits a continuous
band of radiation from 200 1000 nm.
• Not very common because they are expensive and have a short lifetime.
B. Components of UV-Vis Spectrometers
2. Sample containers are usually cuvettes.
• Constructed of either quartz or glass.
- Glass is used for the visible region because it is transparent from 350
2000 nm.
- Quartz (silica) is used for the UV region because it is transparent below
350 nm.
• Cuvettes are commercially available
in pathlengths of 0.1 10 cm.
3. Detectors
• Use either a photomultiplier tube or a diode array.
B. Some Typical Instruments
• Two major classifications of instruments:
1. 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.