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RICHA TRIPATHI 101101111 B-Tech III rd year MANIT Bhopal

Qualitative analysis => Which element is present? Quantitative analysis => How much of the element is present?

Types of X-rays
Characteristic x-rays
elemental identification quantitative analysis

Continuum x-rays
background radiation must be subtracted for quantitative analysis Ratio of Ichar / Ibkg sets limit on elemental detectability

use x-ray energy to identify elements
Quantum mechanics says that the energy of the electron in an atom is quantized and two electrons can never have the exact quantum state nor the same set of quantum numbers according to Hund's Rules

X-ray line energies for each transitions is unique

Moseleys Law
Moseleys Law is the basis for elemental analysis with EDS The energy of the characteristic radiation within a given series of lines varies monotonically with atomic number. This is Moseleys Law: E = C1 (Z- C2)2 where: E = energy of the emission line for a given X-ray series (e.g. K)

light elements will emit X-rays of the K series only intermediate elements will emit X-rays of the L series or K and L series heavy elements will emit Xrays of the M series or L and M series.

Modern X-ray spectrometers are equipped with computer software that is fully capable of identifying the possible elements from a spectrum. The computer software will mark peak positions of the input elements in the spectrum

Computer generated graph

Determination of Intensity of X-Rays

SIGNIFICANCE Intensity of X-Rays of a given element is indicative of its relative concentration

Quantitative Analysis
use integrated peak intensity to determine amounts of elements The concentrations of elements is related to their peak intensities in the spectrum by the relation: C = M K Ir weight fraction (C) of an element relative intensities of its peaks (Ir) instrument factor (K) matrix factor of specimen (M).


The instrument factor K includes conditions of primary sources, the geometrical arrangement of specimen with respect to radiation and detection, and detector characteristics

The matrix factor refers to the interactions among the elements in the specimen. There are three main matrix effects in XRF: primary absorption, secondary absorption and secondary fluorescence.

Primary absorption refers to the radiation that is absorbed on the beams path to reach the atoms to be excited
Secondary absorption refers to absorption of fluorescent radiation from atoms that occur along its path inside the specimen to the detector
Secondary fluorescence

refers to the fluorescent radiation from the atoms which are excited by the fluorescent radiation of atoms with a higher atomic number in the same specimen
Atom of element A Atom of element B Atomic number of A>B

Internal Standard Method

based on the analysis of known standards. Standards should have similar elemental abundances to the sample based on the assumption that the instrumental and matrix effects are the same for the standard and the element to be analyzed Cx / Cs = Ix / Is

For XRF, an uncommon element such as rhodium (Rh) is often selected as the standard material of X-ray tube in order to reduce confusion in Identifying elements in samples.

Some elements show a significant discrepancy. How to make for this? The general formula of quantitative analysis with a standard is expressed by an equation that includes matrix effects. Cx/ Cs = (ZxAxFx) Ix/ Is
The expression (ZxAxFx) represents the matrix factors affecting the X-ray intensity of element and standard.

Z: Atomic Number Effect:

Two factors must be considered regarding atomic number: the backscatter coefficient and stopping power (S) (rate of energy loss) The backscatter coefficient increases with atomic number.The primary electrons backscattered do not generate X-rays. The rate of energy loss due to inelastic interaction increases with decreasing atomic number S = (1/) dEo/ds

A: X-Ray Absorption Effect:

Factor (A) counts the decrease in density of characteristic X-rays from emitting location to detector. The ratio of the measured X-ray intensity to the generated X-ray intensity at some position in the sample is given by Beers Law: I/Io = exp (-m d) where: I/Io = fraction of X-rays transmitted; d = thickness; = specimen density; m = mass absorption coefficient

F: X-Ray Fluorescence Effect:

For example, in a Cu-Fe sample, Cu K radiation (8.04 keV) is of sufficient energy to excite Fe K radiation (Ka = 7.11 keV). As a consequence, the measured iron intensity would be enhanced due to fluorescence by copper, while the copper intensity would be suppressed due to strong absorption by iron. The fluorescence factor is usually least important in the matrix factor

Elemental detectability 0.1 wt%-1 wt%, depending on the specimen Energy Resolution 130 eV Peak/Background : 100 in EDS; 1000 in WDS

EDS cannot detect the lightest elements, typically below the atomic numberof Na Cannot distinguish between various isotopes of elements Cannot distinguish between different ions of the same element