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LECO
LECO
Calculate Area
The final output signals, whether baseline corrected, wedge rule
corrected, or uncorrected, are used to determine a raw peak area,
Arange, for each analyte range. This raw area is reported in the
expanded replicate information in the Cornerstone® brand software.
Further corrections, as follows, are applied to the raw total area
before they can be used with a calibration.
Adjusted Area
The adjusted area, Aadj, range, corrects the raw area for
sensitivity factors and blank values.
Blan
k
The blank value, Ab,range, is the average raw area from a set of
samples (empty crucibles, boats, etc.) determined by the user. The
blank value is used to account for analyte gases that are repeatedly
introduced through consumables or atmosphere. The default blank
value is 0
1 n
Ab,range ∑Arange
n 1
where n is the number of blank samples as selected by the user.
Sensitivity Factor
The sensitivity factor, Fsensitivity, is a factor that maintains a calibration
slope near 1. It is used to ensure consistent slopes across all
products, so it is easy to determine when cell sensitivity (the slope) is
incorrect. It enables better instrument troubleshooting, though the
use of the sensitivity factor means the instrument sensitivity cannot
be determined from the calibration slope.
A sensitivity factor is determined for each detector in an instrument
and may vary with software version.
Adjusted Area
The adjusted area can be calculated as follows:
Aadj,range range ∑ ∑ sensitiviyt
Ab,range
Determine Range
This section is applicable only to dual-range instruments.
If an instrument utilizes both a high and low range for a given analyte,
the correct mass result must be used. The result may come from the
high range, low range, or a blend of both depending on the method
settings.
If a blended result is desired, the value is determined based on the
high and low range thresholds set by the user (ThH and ThL) and the
maximum peak height of the low range result for each analysis (Hp).
If:
Hp > ThH, Use high range
Hp < ThL, Use low range
ThL < Hp < ThL, Use blended results, detailed as follows:
The peak height is reported in the expanded replicate information in
the Cornerstone brand software.
where G (grams) is the analyte mass for a given cell and the k values
are constants determined in the calibration. The adjusted area is
used and the mass result is calculated. For instruments with multiple
ranges, the analyte mass is usually calculated for each range.
Drift Correction
The drift factor, Fdrift, corrects for day-to-day changes in signal due to
changing environmental, matrix, or sample conditions. It is a simple
multiplicative factor applied to the final analyte mass and reduces
the frequency with which new calibrations need to be set. The drift
factor value is determined against a calibration and has a default
value of 1.
Gdrift G ∑Fdrift
∑Th H ∑Th L ∑
Thorough calibrations are required at both the low and high ranges to
optimize signal blending.
Determine Concentration
The determined analyte mass, G or Gblended, is used in conjunction
with the sample mass to determine the analyte concentration.
Calibration Coefficient
Calculated for Each
k The best-fit coefficients determined weighted least Calculated
Method
squares
n The number of replicate samples included in the Calculated Calculated for Each
calibration. Calibration
Calibration Equation
A weighted least squares algorithm is used to determine
the polynomial coefficients, k.
W ∑Aadj k 0 k1 ∑G
∑G
Apply Calibration
Given the coefficients, K, the determined analyte mass, G, can be
determined for each replicate by solving the following equation:
Aadj k 0 k1 ∑G
Weighting Factors
Weighting factors, W, are calculated as:
g ∑wi
Wi 2
0.0001 g i
where
1 n
g ∑g i
n 1
g is the certified analyte mass for each replicate, i, included in the
calibration and w is a user entered weighting factor. By default, the
user defined weighting factors, w, are set to 1.0. If the higher order
calibration option is enabled, the operator can view and edit the
weighting factors.
Calibration Statistics—RMS Error
The Root Mean Square Error (RMS) is a measure of the accuracy of
the calibration. The accuracy of the calibration improves as the RMS
Error approaches zero.
The RMS Error is determined as:
n 2
∑ g
RMS Error (g) ∑ gi,certified
i,measured
1
n ∑∑
– gi,certified
n
2
∑ g i,measure
R 1 ∑ 1
n
d
2
∑ g i,measure –g
1 d
Override Conditions
When possible, Cornerstone brand software chooses a Regression
Order of “Linear” and a Regression Type of “Full Regression”
whenever a new calibration equation is created.
To prevent invalid calibration equations, the software will
automatically override user settings and defaults to ensure that a valid
calibration equation is determined. The following criteria are used:
Single Cluster
No matter how many replicates are included, calibrations that are
recognized as a single cluster of measurements will automatically be
set to a Regression Order of “Linear” and a Regression Type of
“Force Through Origin.”
The calibration data will be interpreted as a single cluster if any of the
following criteria are true:
• The range of analyte present in the calibration data is less than
three times the range of the absolute error (g) of the
calibration.
max analyte(g)cert ∑min analyte(g) cert 3 ∑max Errorg ∑min Errorg
• The minimum amount of analyte is greater than 80% of the
maximum amount of analyte included in the calibration
data.
max analyte(g) cert 80% ∑max analyte(g) cert
• The slope is negative.
Slope0
Cornerstone Brand Software Rounding
NC 450
2 LPM cc/min
Dose Dose B
Gas S
B V
High
NO
10
S Bypass
20 psig
NO
V NC CO2
SV312 10
55 psig R32 R
2 COM
L
NC 1
P
2 LPM
Dose A Bypass
R
G CO Legend
T
Dose Incoming Leak Check
Gas Segment
FL
A 55 psig
T
R Analyze Leak Check
20 psig Heat Segment
ed
Reag Furnace Leak Check
ent Segment (Bypassable)
FL 650°
He T C
R
Copp
20 psig er
S Electrode Oxid
V Furnace
10
NC
P
T
P
Coolant System
Bypass H2O
Inco
min
g
Bypass Low CO2
Purif
ier
650°
C PV1 Flow
Copp COM
Scru
S
V
NO
bber
10 Leco
NC
Inco sorb/
min Anhy
g
O dron
MI
Scr e
PT2
ubb P
er NC R3
S SV108
Leco NO
Exhaust
NO
V 5000
sorb/ MeFC1
10 cc/min
Anhy COM 35 cc/min
TC
Figure 7-1
Linear Flow Diagram (ONH836)
Theory of Operation 836 Series 7–15