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Electromagnetic spectrum

Single and Double Beam Spectrometer

Single-Beam: There is only one light beam or optical path from the source through to the detector. !! Double-Beam: The light from the source, after passing through the monochromator, is split into two separate beams-one for the sample and the other for the reference.
!!

Spectrometers (single beam)

Spectrometers (double beam)

Components of a Spectrophotometer Light Source

!! Deuterium

Lampsa truly continuous spectrum in the ultraviolet region is produced by electrical excitation of deuterium at low pressure (160nm~375nm) !! Tungsten Filament Lampsthe most common source of visible and near infrared radiation.

Deuterium lamp

Tungsten lamp

Components of a Spectrophotometer

Monochromator
!! Used

as a filter: the monochromator will select a narrow portion of the spectrum (the bandpass) of a given source in analysis: the monochromator will sequentially select for the detector to record the different components (spectrum) of any source or sample emitting light.

!! Used

Monochromator Czerny-Turner design

Grating

Detector Barrier Layer/Photovoltaic

Principle of Barrier Layer/ Photovoltaic Detector

This device measures the intensity of photons by means of the voltage developed across the semiconductor layer. !! Electrons, ejected by photons from the semiconductor, are collected by the silver layer. !! The potential depends on the number of photons hitting the detector.
!!

Detector Phototube

Principle of Phototube Detector

This detector is a vacuum tube with a cesiumcoated photocathode. !! Photons of sufficiently high energy hitting the cathode can dislodge electrons, which are collected at the anode. !! Photon flux is measured by the current flow in the system.
!!

Detector Photomultiplier

Principle of Photomultiplier Detector

The type is commonly used. !! The detector consists of a photoemissive cathode coupled with a series of electronmultiplying dynode stages, and usually called a photomultiplier. !! The primary electrons ejected from the photocathode are accelerated by an electric field so as to strike a small area on the first dynode.
!!

Principle of Photomultiplier Detector

The impinging electrons strike with enough energy to eject two to five secondary electrons, which are accelerated to the second dynode to eject still more electrons. !! A photomultiplier may have 9 to 16 stages, and overall gain of 106~109 electrons per incident photon.
!!

Quantitative Analysis

Transmittance and Absorbance

Example: A sample has a percent transmittance of 50.0%. What is its absorbance?

With a percent transmittance of 50.0%, the transmittance of the sample is 0.500. Substituting into equation gives! ! A = log T = log(0.500) = 0.301!

Absorbance and Concentration

Example: A 5.00 ! 104 M solution of an analyte is placed in a sample cell that has a pathlength of 1.00 cm. When measured at a wavelength of 490 nm, the absorbance of the solution is found to be 0.338. What is the analytes molar absorptivity at this wavelength?

SOLUTION Solving equation for and making appropriate substitutions gives

Multicomponent samples

Transmittance
I dI T= " = kcdb I0 I0
b dI #I0 I 0 = !kc #0 db I

I0

I I " ln( ) = !kbc = 2.303 log( ) I0 I0 I " ! log( ) = ! log T = A = $bc I0 k $= 2.303

Limitations of Beers Law

Calibration Curve (External Standard)

Regressi Linear Equation

No
1 2 3 4 5 6 7

X
0 2 4 6 8 10 12

Y
2,1 5,0 9,0 12,6 17,3 21,0 24,7

XY

X2

Y2

"X

"Y

"XY

"X2

"Y2

Standard Addition Method

!! Standard

addition must be used whenever the matrix of a sample changes the analytical sensitivity of the method. !! In other words, the slope of the working curve for standards made with distilled water is different from the same working curve.

Prepare the Standards

The concentration and volume of the stock solution added should be chosen to increase the concentration of the unknown by about 30% in each succeeding flask.

A = ! bC

! bVxCx ! bVsCs A= + = kVxCx + kVsCs Vt Vt y = a + bx (b = kVs , x = Cs , a = kVxCx ) VsCs A = 0 ! kVxCx = "kVsCs ! Cx = " Vx
Cx: unknown concentration

Contoh: Diketahui: Volume sampel (Vx) = 10,0 mL Volume labu takar (Vt) = 50,0 mL Konsentrasi standar (Cs) = 150 g/mL
Vs yang ditambahkan (mL)

10

15

20 9,06

Absorban

3,06 4,56 6,06 7,56

Hitung konsentrasi sampel (Cx)

Hasil perhitungan: b = 0,10 a = 3,06 r = 1,00000 Persamaaan garis : Y = 3,06 + 0,10X Jika Y = 0, maka Cx = 30,6 g/mL

Multicomponent analysis