‫دانشگاة آزاد اسالمى واحد علوم وتحقيقات‬

Elemental Analysis

Sajad
Sajad Mohammad
Mohammad Aklo
Aklo
 Presentation Diagram

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PREFACE C/H/N/S-Analysis
The Purpose of EA
EA Divisions Definition
Type Of Analysis Elemental Basic Principle
General Information Analysis Applications

Definition
Dumas Method Definition
Measuring Principle EA Schematic
Gases And Reagents Applications
Proplems Chanlenges

C/H/N-Analysis CHNS/O-Analysis
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2 Gas Separation And Standards

 PREFACE
The purpose of elemental analysis is to determine the quantity of a particular element within a
:molecule or material. Elemental analysis can be subdivided in two ways

.Qualitative: determining what elements are present or the presence of a particular element
.Quantitative: determining how much of a particular or each element is present

In either case elemental analysis is independent  

of structure unit or functional group, i.e., the
determination of carbon content in toluene
does not differentiate between ) C6H5CH3 (
the aromatic carbon atoms and the methyl
.carbon

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 PREFACE
:The Difference Between The Types Of Analysis

:Qualitative Analysis
Gives information only on whether or not a compound or element is present -1
Often inexpensive, manual method -2
Usually requires large amount of sample (mg-mg)-3

:Quantitative Analysis

Measures the exact amount of compound present in the sample -1

Performed for a known sample-2
Often requires high accuracy and precision -3

Semi-Quantitative Analysis
Identifies presence or absence of element or compound -1
Provides some crude measure of the amount of compound present (i.e.,-2
screening method)

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 PREFACE
Elemental analysis can be performed on a solid, liquid, or gas. However, depending on the
technique employed the sample may have to be pre-reacted, e.g., by combustion or acid digestion.
The amounts required for elemental analysis range from a few gram (g) to a few milligram (mg) or
.less

Elemental analysis can also be subdivided into general categories related to the approach involved
.in determining quantities

Classical analysis relies on stoichiometry through a chemical reaction or by * .1

.comparison with known reference sample .2

Modern methods rely on nuclear structure or size (mass) of a particular element and are *
.generally limited to solid samples

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 C/H/N-Analysis

A CHN Analyzer (also known as a carbon hydrogen and nitrogen analyzer) is a scientific
instrument which is used to measure carbon, hydrogen and nitrogen elemental concentrations in a
.given sample with accuracy and precision

Sample sizes are most often just a few milligrams, but may differ depending on system. For some
sample matrices larger mass is preferred due to sample heterogeneity. These analysers are capable
of handling a wide variety of sample types, including solids, liquids, volatile and viscous samples,
.in the fields of pharmaceuticals, polymers, chemicals, environment, food and energy

This instrument calculates the percentages of elemental concentrations based on the principle of
"Dumas method," using flash combustion of the sample to cause an instantaneous oxidization
into simple compounds which are then detected with thermal conductivity detection or infrared
.spectroscopy.Separation of interference is done by chemical reagents

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 C/H/N-Analysis
?What Is Dumas method
The method consists of combusting a sample of known mass in a high temperature range of 800-
900°C chamber in the presence of oxygen. This leads to the release of carbon dioxide, water and
nitrogen. The gases are then passed over special columns (such as potassium hydroxide aqueous
solution) that absorb the carbon dioxide and water. A column containing a thermal conductivity
detector at the end is then used to separate the nitrogen from any residual carbon dioxide and
water and the remaining nitrogen content is measured. The instrument must first be calibrated by
analyzing a material that is pure and has a known nitrogen concentration. The measured signal
from the thermal conductivity detector for the unknown sample can then be converted into a
nitrogen content. As with the Kjeldahl method, conversion of the concentration of nitrogen in a
sample to the crude protein content is performed using conversion factors which depend on the
.particular amino acid sequence of the measured protein

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 C/H/N-Analysis

Measuring Principle
The sample under test is weighed in using a tin capsule. The required amount is 2 to 3 mg of
organic material and can hardly exceed 10 mg, if inorganic matter with little carbon content is
investigated. After folding the capsule (looking rather like wrapped tin foil) the sample is placed
.in the autosampler

The tin capsule enclosing the sample falls into the reactor chamber where excess oxygen is
introduced before. At about 990 °C the material is "mineralized". Formation of carbonmonoxide is
.probable at this temperature even under these conditions of excess oxygen

The complete oxidation is reached at a tungsten trioxide catalyst which is passed by the gaseous
reaction products. The resulting mixture shoulöd thus consist of CO2, H2O und NOx. But also
.some excess O2 passes the catalyst

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 C/H/N-Analysis

Measuring Principle
The product gas mixture flows through a silica tube packed with copper granules. In this zone
held at about 500 °C remaining oxygen is bound and nitric/nitrous oxides are reduced. The
leaving gas stream includes the analytically important species CO2, H2O und N2. Eventually
.included SO2 or hydrohalogenides are absorbed at appropiate traps

High purity helium (Quality 5.0) is used as carrier gas. Finally the gas mixture is brought to a
defined pressure/volume state and is passed to a gas chromatographic system. Separation of the
species is done by so called zone chromatography. In this technique a staircase type signal is
.registrated. Step height is proportinal to the substance amount in the mixture

A modern CHN Analyzer

.constructed in 2011

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 C/H/N-Analysis
Chemicals and Reagents
Gases
 Helium (carrier gas): chromatography grade
 Oxygen (sample oxidation gas): 99.995% minimum purity

Reagents
Note that many of these materials are hazardous and before any work is done with
them, the user must be familiar with the appropriate Material Safety Data Sheets
) .(MSDS)

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 C/H/N-Analysis

Problems and Interferences:

The weighing of oily or fluid substances is impossible using the thin walled tin
capsules. For this purpose alumina pans with a lid are available. These pans are tightly
closed by cold welding to prevent loss of sample by spillage and evaporation. As the
blank value for nitrogen is dramatically increased be the enclosed volume of air the
.%-determination limit for N in liquid samples is increased to 0,1 to 0,2 w
With highly viscous or even glassy materials elemental analysis is even impossible
with the above method

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 C/H/N/S-Analysis
CHNS elemental analysers provide a means for the rapid determination of carbon, hydrogen,
nitrogen and sulphur in organic matrices and other types of materials. They are capable of
handling a wide variety of sample types, including solids, liquids, volatile and viscous samples, in
.the fields of pharmaceuticals, polymers, chemicals, environment, food and energy

In its simplest form, simultaneous CHNS analysis requires high temperature combustion in an
oxygen-rich environment and is based on the classical Pregl-Dumas method. This combustion
can be carried out under both static conditions i.e. introduction of a set volume of oxygen or
dynamic conditions i.e. a constant flow of oxygen for a set period of time. Often, catalysts are also
.added to the combustion tube in order to aid conversion

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 C/H/N/S-Analysis
BASIC PRINCIPLES

In the combustion process (furnace at ca. C), carbon is converted to carbon dioxide; hydrogen  
.to water; nitrogen to nitrogen gas/ oxides of nitrogen and sulphur to sulphur dioxide

If other elements such as chlorine are present, they will also be converted to combustion
.products, such as hydrogen chloride

A variety of absorbents are used to remove these additional combustion products as well as some
of the principal elements, sulphur for example, if no determination of these additional elements
.is required

The combustion products are swept out of the combustion chamber by inert carrier gas such as  
.helium and passed over heated (about C) high purity copper

This copper can be situated at the base of the combustion chamber or in a separate furnace. The
function of this copper is to remove any oxygen not consumed in the initial combustion and to
convert any oxides of nitrogen to nitrogen gas. The gases are then passed through the absorbent
.traps in order to leave only carbon dioxide, water, nitrogen and sulphur dioxide

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 C/H/N/S-Analysis
BASIC PRINCIPLES
: Detection of the gases can be carried out in a variety of ways including

a GC separation followed by quantification using thermal conductivity detection )i(

a partial separation by GC (‘frontal chromatography’) followed by thermal conductivity )ii(

detection (CHN but not S)

a series of separate infra-red and thermal conductivity cells for detection of individual )iii(
.compounds

Quantification of the elements requires calibration for each element by

using high purity ‘micro-analytical standard’ compounds such as
.acetanilide and benzoic acid

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 C/H/N/S-Analysis
Applications of CHNS Elemental Analysers

CHNS elemental analysers have been used in analytical laboratories for over thirty years. The
method is used extensively across a wide range of applications, including pharmaceuticals,
.chemicals, oil-related products, catalysts and food

In the oil industry, an important application is the regular monitoring of coke build-up on refinery
catalysts to ensure that regeneration procedures (involving controlled burning of the carbon) are
.executed at optimal intervals

Since many of these catalyst systems involve large quantities of noble metals such as platinum,
.palladium and rhenium, mismanagement of this testing would entail serious financial losses

In food analysis, the determination of nitrogen (as a surrogate for protein) is very important for
pricing grain and evaluating meat products, and is increasingly undertaken by combustion
.analysis

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 CHNS/O-Analysis

also known as organic elemental analysis or elemental microanalysis, determines the

amounts of Carbon (C), Hydrogen (H), Nitrogen (N), Sulfur (S) and Oxygen (O)
present in a sample. ... are measured using gas chromatography and thus the ratio of the
.elements in the original sample is determined

The end products of the combustion would be mostly the oxides of theconcerned elements in the
form of gases. These are then separated and carried to the detectorusing inert gases like helium or
.argon

.CHNS/O configuration
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 CHNS/O-Analysis
Elemental Analyser Schematic

Autosampler
He
O2 Gas chromatography
Column in oven

-Thermal Conduc
tivity Detector
Water
Trap EA line
TCD out

CO2
N2
Combustion Reduction
Chemicals H2O
Chemicals SO2
1020C 650C
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 CHNS/O-Analysis
Applications of CHNS/O Elemental Analysers

Pharmaceutical / Chemical: confirmatory analysis, purity -1

Energy: C/H Ratio of fuel, BTU analysis of coal, impurities analysis -2

Polymers: blend analysis, nitrogen level -3

Environmental: C/N ratio in soil, sediment and plant material, organic particulate collected on -4
filters, nitrogen content in fertilizer

Food / Animal Feed: protein content, product labeling -5

Explosives: nitrogen content-6

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 CHNS/O-Analysis
The Challenges of CHNS(O) Analysis

Weighing out very small quantities into minuscule containers is fiddly and must be done with -1
care. As the final results of C, H, N and S content is given as a percentage of the initial sample
.weight, it is critical to weigh the sample accurately and record the weight correctly

Because many samples of the same substance will be analyzed, using small sample sizes -2
minimizes substance use, reduces the amount of oxygen required for combustion, and decreases
.waste. A balance with a low minimum weight helps to minimize the amount of substance required

Preparing samples for CHNS(O) analysis is a time and labor-intensive process. Microbalances -3
.are very sensitive and can take several seconds to settle before releasing the weight result

Transcribing results takes time and is prone to human error, especially when weight results have -4
6 or 7 decimal places. Traceability of results is important to labs carrying out the analyses as well
.as to the end-customers

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 GAS SEPARATION

Helium Carrier Gas Pushes Combustion Gases Through Analyser . .Argon Os

Alternative Gas

C , H And S Combustion Gases Are Trapped In Separate Columns , .Then

Sequentially Released (Purge And Trap )

N2 Gas Is Not Trapped . It Flows Straight Thru Columns

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 STANDARDS
The Standards Selected Cover A Large Range Of Concentration From .4.84 To 46.65
% Nitrogen And From 20 To 71.09 % For Carbon

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 THE END

THANK YOU

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