2400 Series 2

CHNS/O Analyser
Paul Gabbott PETA

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Organic Elemental Analysis

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The PE 2400 CHNS/O Elemental Analyzer is a combustion technique that determines weight
percent carbon, hydrogen, nitrogen, sulfur or oxygen in a variety of sample types

Capable of operating in 3 modes; CHN, CHNS and Oxygen

Organic Elemental Analysis

The 2400 is an organic elemental analyser
It is designed to analyser organic materials such as those produced in
a chemical laboratory
It is not designed for inorganics eg carbon in steel
Nor is it a TOC analyser (total organic carbon). In some instances the
2400 could act as a TOC but it is not designed to continuously handle
applications such as TOC in seawater

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How does it work ?

Combustion technique
Typically a sample is weighed into a tin capsule and placed in the
autosampler carousel.
Information is entered into the instrument (ID & wt) and the run started.
The sample is combusted into simple gases, CO2, H2O and N2, collected
in the mixing chamber, separated by frontal chromatography and
measured by TC

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2400 Design Schematic

Combustion Zone

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Gas Control Zone Separation

Detection

Combustion Process

Completely combusting a weighed sample is critical to obtaining

accurate results

Static and Dynamic

4 steps to combustion
Sample introduced into oxygen environment
Additional oxygen introduced
Allowed to sit and burn
Additional oxygen introduced
Operator programmable

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CHN Combustion Tube

Combustion Tube
Ultra high gases and pure quality reagents are required

Oxidizing & Removes interferences

i.e.,halogens and sulfur
Aids in the combustion of the sample
Prevents unwanted elements from interfering with the
analysis and keeps the system cleaner

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CHN Reduction Tube

Combustion and Reduction Packing

Combustion Tube
Silver Vanadate
Silver Tungstate
EA-1000

Reduction Tube

Copper 60-80 mesh

Pack the Copper as tight as you can
Cuprox
Copper Plug
Leave about inch space from top of
copper plug and the top of the tube

Reduction Tube
Removes excess oxygen
Reduces NOX to Nitrogen
Copper oxide at the end converts any CO to CO2
Operates at about 640C (the best temp is often debated)

Consumables
Consumables are supplied
individually or in kits

N241-0680 CHN
Combustion Kit
2 Combustion tubes &
Chemicals 2000 runs

N241-0681 CHN
Reduction tube Kit
2 tubes 500 runs total

Gas Control Zone

Homogenous mixture of product gases will achieve the highest precision

Constant temperature, volume and pressure maintained in the mixing chamber

Environmental conditions such as changes in barometric pressure do not affect results
Achieve highest precision
Separates the combustion area from the separation area , so we can change the amount
of O2 without change in retention times
Mechanical mixing
Ensures a homogenous mixture of product gases

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Separation

Frontal Chromatography
Steady State Signal
Simple difference calculation determines signal
Easier to calculate a small step change than a small peak

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Frontal Chromatography

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Modes of Operation

CHN mode is the most universal of the analysis

CHN mode has the best reagent design and allows use of the Optimize Combustion
control parameters.
Interfering elements (halogens and sulphur) are removed.

CHNS mode designed to include sulphur, which reduces universality. This includes
limiting the range of sample types and sample size (1 to 2 mgs recommended). Metal
cations are excluded.
Special care must be used in calibration and blanks for lower levels of sulphur.
The Oxygen mode where oxygen in a sample is converted to carbon monoxide over
platinised carbon.
This mode excludes compounds containing phosphorous, fluorine, silicon and metal
cations. Samples containing mineral matter must be demineralised prior to analysis.
Upgradeability The user may choose any or all modes. The 2400 Series II may be freely
upgraded at any time to add additional mode capability to suit the needs of the
laboratory.
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Sulphur

CHNS is determined in a similar manner to CHN

Sulphur separates after water so gives a step after water
This gives a longer analysis time
However the combustion tube is completely different

Sulphur Tube

Operating
temperature
around 975C

Sulphur tube
Sulphur burns to SO3 and SO2
The SO3 must be removed (reduced) immediately because of
its reactivity
This is achieved by adding copper to the combustion tube
Normal catalysts are replaced with EA 6000 because they
scrub for sulphur
Dynamic combustion conditions are required, and this restricts
the use of the ability to extend combustion time or add extra
oxygen
CHNS does not use a separate reduction tube

Oxygen Analysis
Oxygen is converted to carbon monoxide over platinised carbon
in a helium gas stream using silver capsules.
Helium / hydrogen (approx 5%) gas stream enhances conversion to
CO and allows the use of tin capsules.
Copper is used to convert any CO2 formed back to CO

Acid gases are scrubbed in a trap installed on the side of the

analyser

Oxygen Tubes

Trap used with oxygen

Oxygen detection

Oxygen applications
Often involve coals or fuels
Note that coals must be demineralised for which procedures exist, but
it is not as simple.

CHNS and O2

CHNS Tubes
Copper
EA-6000

Oxygen Tubes
Copper

Analysis Times
Analysis times CHN: 6 min, CHNS: 8 min, Oxygen: 4 min
Sample size 0 to 3 mgs typically depending on sample type. Small
samples will generally be limited by weighing errors, but may be used.
Large samples may be used if the combustible content is low

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Analytical Element Range (mgs)

detector range
C 0.001 - 3.6 S 0.001 - 2.0
H 0.001 - 1.0 O 0.001 - 2.0
N 0.001 - 6.0

Capabilities of EA 2400 Data Manager

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Collect and store complete run information

Search stored runs
Create reports
21 CFR part 11 compliant option
audit trail
signature points
permissions
Complete analyzer history stored
Instrument messages
Leak test output
Timing events
Monitored components
Advanced calculations
Statistics
Recalculation capabilities
Archive data

EA 2400 Data Manager Main Run Window

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Queries
Specify your search using
AND/OR statements on
sample ID
date
operator
project
run type
mode
Set limits like
is
contains
does not contain
starts with
between
before
after
on

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Advanced calculations and Statistics

Advanced calculations
provide additional
information on results

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Statistics can be
preformed on a
set of runs

Printing reports and exporting data

Print
Table
Report template

Save to a file
RTF
TXT
PDF

Export formats
Excel
CSV

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Diagnostics
For confidence in instrument performance and for easy
evaluation of instrument history the operator can send vital
information to the database, including
Instrument status
temperatures
pressures
detector signals
voltages
Leak test results
Parameter settings
Purge times

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21 CFR part 11 compliance

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EA 2400 CHNS/O Analyzer

Unique technology features and newest most modern Data
Manager Software

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EA 2400 CHNS/O Analyzer

Operating the system

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Purging the analyser

Blanks
Conditioners
K-Factors
Samples

CHNS and CHN Purge Gases

Gases : Helium and O2 @ 99.995 %

N2 or Air for the Pneumatics @ 99.95 to 99.99%

Purging prior to analysis

The analyser uses helium as a purge gas and oxygen as a
combustion gas
Purge gases contain amounts of carbon, hydrogen and nitrogen which need to
be determined.

In addition contaminants from the atmosphere get into the instrument

and gas lines, particularly overnight and when the system is left
unused.
Purging is required to make sure the analyser and gas lines are free
of contamination before starting.
The longer the gas lines the longer the purge times
Oxygen is used only as required so the oxygen lines are more prone to
contamination when the system is unused

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System Purging
Helium purge
Use as long as found necessary to purge the analyser
Afterwards a series of helium blanks can be performed to ensure the analyser
is free of contaminants

Oxygen Purge
Oxygen purging will pass through the copper tube and can cause a significant
loss in lifetime of the copper
Oxygen purging should be kept to a minimum
The end of the combustion tube may be loosened to allow oxygen escape
before the reduction tube.

Gas Lines
These must be copper or steel and completely free of leaks. Any leaks will
seriously compromise performance. As a result gas lines must be connected
straight to a cylinder and not used by any other equipment whatsoever.

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Leak tests
Leak Tests
#1 Mixing Volume
#2 Combustion /Auto-Injector
#3 Column/Detector
Must pass Leak test 1
Pressure should get to 760 mm,
you will here a click around
730mm. Pressure will hold for 5
mins @ 760 mm.
Test 2 will pressure around 780
to 800 mm, you may get a small
drop in pressure +/- 2 mm
If this fails Check for Cracked
tubes, Auto-injector o-rings

Leak Tests
Leak test 3 adds the
detector and column
Cap sensing vent
Sensing vent is the peek
tubing a yellow heat shirk
tubing on it

Blanks
Blanks consist of running the system without any sample to determine
background levels of contamination. These are then subtracted from the
sample values.
Tin (and all other) capsules contain levels of impurities which must be
measured so need to be included.
Full oxygen blanks contain everything except a sample
They use up copper at a high rate so should be kept to a minimum
Helium blanks are run without oxygen or a capsule and are used to make
sure the system is purged, stable and ready to be used. They do not use up
chemicals so can be used freely.

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Conditioners
Blanks decondition the system by removing adsorbed water from internal
surfaces
A series of blanks will therefore continuously reduce the hydrogen
background value
Any sample run afterwards will show lower levels of hydrogen than it
should because some of the water will be used to re-establish the
adsorbed water equilibrium.
As a result a conditioner must be run after a blank .
Normally this is a sample of the reference standard
It does not have to be weighed because no use will be made of the
result, but normally this is good practice to make sure a sensible
amount is used, (eg 2mg similar to a sample)

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Blank Values
Blank values are determined from a running average of
three blanks interspersed with conditioners. The
system automatically averages the results unless blanks
are run sequentially
The manual makes the following comments

K Factors
K Factors are the calibration factors determined for each
element by running known standards.
The step height of the signal for each element is measured in
microvolts per microgram (or whatever units the software uses)
of element present.
Sample response divided by the K Factor allows the amount of
each element to be determined. This is converted to a weight
percent when the weight is known.

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K Factors
K factors are determined from the running average of three
or more values. Typical values as given by the manual are
shown below.

K-factors
K-Factors
should be run periodically to account for any drift or instability in the
system.

Standards used
Should be appropriate to the samples being run
Eg if a 5% nitrogen standard is run with a 50% sample any error will
be magnified 10 times
Different standards can be used for different elements if required.

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Typical Sart-up Sequence

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Check Leak tests

5 Helium blanks
Conditioner
Blank
Conditioner
Blank
Conditioner
Blank
Conditioner
3 K-Factors
Samples

Samples
Solid samples are
encapsulated in tin foil
capsules which are folded
manually using a pair of
tweezers
Care must be taken not to
tare the foil or lose sample in
this process
This is one of the most
important and time consuming
aspects of analysis

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Weighing Samples
Samples need to be
weighed to at least six
figures (microgram) level
weighing accuracy of a 1mg
sample weighed to 6
figures is +/- 0.1%
weighing accuracy of a 1mg
sample weighed to 5
figures is +/- 1%

Weight range specification

Total weight of each element must not exceed the analytical range below

Homogeneity
Since samples are small they must be representative of the
material they are from
Inhomogeneous samples should be ground and a small amount
of the resulting fines taken
Potentially Inhomogeneous samples include
Polymers and Composites
Coals and minerals
Solis and biological materials

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Liquid Samples
Volatile free flowing liquids can be syringed into small
aluminium capsules (which contain around 2mg material)
sealed, and weighed.
These are then inserted into tin capsules since tin aids the combustion

Non volatile liquids can be inserted into thicker walled tin

capsules.
It is always good to minimise the amount of aluminium put into the
combustion tubes it can wet quartz and cause the tube to crack

Viscous volatile liquids use volatile aluminium pans more

frequently associated with DSC

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Liquid samples
If a lot of aluminium is used
then the quartz tube may
need to be protected. This
can be done using zirconia
cloth, or a sacrificial quartz
inner tube.
Do not cool the furnaces
overnight and replace the
vial receptacle more
frequently

Handling Samples
N241-1255

Standard tin capsules. For solids and viscous, non-volatile liquids

N241-1362 Large tin capsules. For larger sample weights of solids with inert
material (soil, silica beads) and lower carbon.
N241-0320 Volatile tin pans and covers. Requires sealer, 0219-0061. For
volatile viscous liquids i.e. urea formaldehyde.
0240-0642 4 l aluminum capsules. Requires sealer B019-8093. For volatile, nonviscous liquids i.e. gasoline.
0009-0709 30 microliter aluminum capsules. Requires sealer B019-8093. For
volatile, slightly viscous liquids.
N241-1363

Tin disks. For particulate material collected on a glass filter.

N241-xxxx

Thick walled tin capsules for liquids

Accuracy Specifications

Optimise Combustion

Optimise Combustion

For most CHN work the extended combustion time can be set
to 10 20 seconds
Increased oxygen usage should be avoided if not needed since
it reduces the life of the copper tube.

High carbon containing samples

POLYNUCLEAR AROMATICS
These are quite demanding materials due to high Carbon
content and difficult to burn structure. Typically limit max
sample size to about 2.5mg, add extra combustion time
and extra oxygen if incomplete combustion is found.

Incomplete combustion
Quite rare but may occur with very high carbon containing
materials or if the combustion tube needs to be changed
How is this evident
Increasing carbon background (blank)
Production of methane (shows as a high nitrogen / low carbon result)

Remove residue by running some oxygen blanks or Purge with

oxygen to burn any remaining carbon
Extend combustion time and amount of available oxygen for
future runs or reduce sample weight.

High carbon containing samples

Carbon Fibre
Increase combustion furnace to 980C
Max weight around 2mg

Low combustible (carbon) content

SOILS
Soils work well on the 2400 because higher wts can be used
and the furnace conditions can be optimised to burn them.
Samples should be well dried first.
I typically work with approx 20mg samples thought weights
can be higher if required, add 20 seconds to combustion and
add a second to oxyfill and oxyboost1

Coal
Actually it does not burn easily
Needs time and available oxygen, but 20 secs extended combustion
and typically 2 secs extra oxygen are sufficient

Homogeneity is always an issue and how well it is ground

Moisture content is another, usually it is analysed after drying
Usually analysed for its calorific content which is calculated
from its elemental composition

Particulate matter in water or air

This is an increasingly common requirement

Applications include air quality
exhaust emissions
Plankton in seawater

Material is collected on filter discs which can be analysed

completely in the 2400

Rolling up a glass fibre filter disk

Filters

Use a sacrificial quartz liner

Do not drop furnace temps in case of wetting
Extend combustion times
Calculate C/N ratios

Silicon containing compounds

May form a stable silane or the extremely stable silicon
carbide. The general approach to analysis of this type of
material is to add vanadium pentoxide to the capsule if
required. Tin also promotes combustion of this type of
material , one reason for using it.

Refractory carbides

Organometallic compounds
As with silicon containing compounds these are susceptible to
the formation of stable carbides, eg boron carbide which is a
stable glass. The tin capsule acts as a combustion aid but if
difficulties emerge then vanadium pentoxide should be added
to the capsule.

Mercury containing complexes

If mercury compounds are in use then as a precaution add
pelleted gold to the combustion tube to trap any potentially
volatile mercury produced
REPLACE TUBE AFTER THE ANALYSIS HAS FINISHED

Use a similar approach with other potentially hazardous metal

complexes
most will produce stable oxides

The tube catalysts and the copper tube are actually very good
at scrubbing for these products
It is therefore good practice to replace the combustion tube regularly
before any unwanted elements pass through the system

Varying H content
The equilibration effect of water during blanks has already been
noted
It also has an effect as samples are run
High H followed by low H will result in a higher value for the low
H material than it should have.
Low H followed by high H will result in a low value for the latter
material
All results are should still be within specification but these
effects are easily noticeable.

Effect of a hydrate

Water content has a significant effect on results

as shown in this example of a hydrate. Solvates
also have a significant effect.

Effect of Solvate / Hydrate

Calculations exist that allow

the operator to fit the data to
a known solvate. However
the material may not be fully
solvated which causes
difficulties

Effect of moisture

It is no surprise that moisture has a similar effect

If a sample is not dry then accurate CHN data is difficult
It can be back calculated but again this is not ideal
Impure (wet) samples give inaccurate results

Sulphur
CHNS determination works but the system is not as optimised
as for CHN
Additionally the separation of water and sulphur is not complete
This makes determination of low levels of sulphur difficult
unless the water is removed using an in-line trap.

Final practical comments

Drying the catalysts

The EA 1000 and silver tungstate on magnesium oxide are best
dried before use.
Use a muffle furnace at 900C for 30 minutes, longer at lower
temps
Store in a dessicator
Damp material leads to high hydrogen blanks that drift down
and the water evolved can also promote devitrification of the
quartz

Diagnostics-Signal Timing
Make sure signals are properly timed

Signal Timing

Filter Disks

Install Filter disks on both sides of the crossover and at the top of the Reduction tube

This will help in keeping the cross-over and

the parts after the reduction tube clean
Place filters on both side of the cross-over
and the top of the reduction tube

CHN Reduction Tube

Copper reduction tube with
support for filling
If not properly filled this is the
main cause of drift in an
analyser
Wire form copper is easier to
pack but is less efficient
Copper powder gives the
longest life but often settles
in use