Errors in Chemical Analysis

Errors
Precision
The term error has two slightly different
- describes the agreement among several
meanings:
results obtained in the same way.
1. Error refers to the difference between a measured - describes the reproducibility of
value and the “true” or “known” value measurements
- Three terms used to describe the precision of
2. Error often denotes the estimated uncertainty in a
a set of replicate data:
measurement or experiment
• Standard Deviation
“We can only hope to minimize errors and estimate - difference of entry to the
their size with acceptable accuracy” mean of the data set
• Population or Variance
Errors are caused by faulty calibrations or
- how spread out the set of
standardizations or by random variations and
data
uncertainties in results.
• Coefficient of Variation (CV)
Repeated Measurements (Replicates) - Relative standard deviation
- Normalize dispersion in the
- Two or more portions of sample taken
probable distribution
through an entire analytical method
- Compute SD / mean x 100
- Repeated measurements are needed in a
chemical analysis Accuracy
- Characteristics of repeated measurements
- indicates the closeness of the measurement to
“One measurement is no measurement.” the true or accepted value and is expressed by
the error.
Reliability of Data: Accuracy vs Precision
1. Absolute Error (AE)
𝐴𝐸 = |𝐸𝑉 − 𝑇𝑉|
2. Relative Error (%RE)

|𝐸𝑉 − 𝑇𝑉|
%𝑅𝐸 = 𝑥 100
𝑇𝑉

EV = Measured Value
RV = True Value
 Error and Sampling

Error Signal
- cannot be exactly known, but can be Sample Response
corrected and adjusted
- the instrument’s response when the analyte
- the difference between measured value and
is present
true or known value
- the estimated uncertainty in a measurement Blank Response
or experiment
- the instrument’s response when the analyte
Types of Errors in Experimental Data is absent
1. Random (or indeterminate) Error The Signal
- cannot be pointed out easily
- always present, all directions - the difference between the sample and the
- affects precision of measurements blank response
- caused by uncontrollable variable
- cannot be corrected by a blank
- reduced through repeated measurements
- Quantify: Standard Deviation
2. Systematic (or determinate) Error
- affects all measurements in the same
way, direction and magnitude Background or Baseline
- affects the accuracy of the results (RE)
- assignable cause or possible to be
identified
➢ Instrumental errors
• caused by nonideal
instrument behavior,
by faulty calibrations,
or by use under Noise
inappropriate
conditions - A random time-dependent change in the
➢ Method errors instrument’s output signal that is unrelated
• nonideal chemical or to the analyte response
physical behavior of - This tends to make the accurate
analytical systems. measurement of sample, blank and baseline
➢ Personal errors response less accurate
• result from the - Measuring the noise’s intensity in
carelessness, comparison to the signal helps in
inattention or personal determining the accuracy of the
limitations of the measurement and in specifying the detection
experimenter. limit of the signal level one is able to
- Quantify: Bias - measures the systematic measure.
error associated with an analysis. It has Peak-to-Peak Noise
a negative sign if it causes the results to
be low and a positive sign otherwise. - One measure of the amplitude of a sine wave
3. Gross Error is the peak-to-peak amplitude (this is twice
- Occurs occasionally, are often large, and the amplitude which appears in the defining
can cause a result to be either high or low equation for a sine wave)
- Product of human error
➢ Leads to outliers, a value the
lies outside most of the other
values in a set of data
 Error and Sampling

Signal-to-Noise Ratio Thermal Noise or Johnson Noise

Total signal level nor noise level determine
an experiment’s ability to accurately detect an
analyte. Rather it is the ratio of the two that is critical.
The S/N ratio
Shot Noise
𝑁𝑅𝑀𝑆 = 0.354
𝑁𝑝−𝑝 = 0.354 𝑥 10 = 0.035
- Present equally at all frequencies, it arises
due to atoms of solid-state conductor are
vibrating at all temperature and they bump
into electrons. Hence, imposes a new
random motion on those electrons
- Reduce: by cooling it and decreasing the
resistance and by narrowing the
bandwidth/filtered signal. Thermal noise
affects the voltage
- Arise due to charge and energy are
quantized. Slight fluctuation due quantum
nature of things
- Reduce: decrease the bandwidth of the
measurement shot noise affects the current

𝑆 Flicker Noise
= 0.75 / 0.035 = 21.4
𝑁 - The origins are uncertain. Also called pink
Sources of Experimental Noise noise because while it is present at all
frequencies, its intensity drops off as the
1. Chemical reciprocal of the frequency
- Experiments are affected by - Reduce: Measurements taken above 1kHz
uncontrollable environment conditions can neglect flicker noise
affecting the system
2. Instrumental noise Environmental Noise
- Affects all components of the - Also known as interference noise or
instruments electrical pick up. Broadcasting electric and
- Observed noise is a complex composite magnetic fields
of all noise sources - Reduce: by shielding, eliminating ground
loops, rigidly fix all cables and detectors,
isolate from temperature variations,
compensating magnetic fields, etc.
Note: if the Noise is found to be in the detector of the
instrument call the service engineer.

Sources of Instrumental (Electrical) Noise

Family Tree of Error
- Thermal or Johnson Noise
- Shot noise or Quantum noise
- Flicker noise
- Environmental or interference noise
Noise in Measurements
- Unavoidable
- Generally independent of signal size
- S/N <2.3; signal not detectable from noise
 Error and Sampling
Sampling and Associated Uncertainties
Sample
- A portion of material/population
- Selected in a specialized manner
- Sample should:
➢ Represent the whole system
➢ Have a size that could be handles by
sampler/analyst with ease
➢ Retain the properties of the lot (or
change the same way as the lot)
➢ Be suitable to provide needed
information
Sample Size
Sampling
- Taking a portion, using a specified method,
to represent a much larger material
- Results in DECREASED sized of material,
while PRESERVING physical/chemical
properties
➢ Why sampling?
- The limited capacity of analytical
systems
- The destructive nature of analytical
operations
➢ Importance
- Results from the small portion (sample) is
applied to the bulk
- Decision is made depending on results
obtained from testing the sample
“The Analytical Result is no better than the sample
it is based on.”
Sampling error contributes to the overall or total
variance of an analysis
2 2 2
𝑆𝑜𝑣𝑒𝑟𝑎𝑙𝑙 = 𝑆𝑠𝑎𝑚𝑝𝑙𝑒 + 𝑆𝑚𝑒𝑎𝑠𝑢𝑟𝑒𝑚𝑒𝑛𝑡
2 2
If 𝑆𝑠𝑎𝑚𝑝𝑙𝑒 > 3 𝑆𝑚𝑒𝑎𝑠𝑢𝑟𝑒𝑚𝑒𝑛𝑡 , further effors
to reduce the overall error by reducing measurement
error will be useless.
2
If 𝑆𝑠𝑎𝑚𝑝𝑙𝑒 is large, the measurement method
need not be accurate since the overall error is already
greatly affected.
 Error and Sampling

Sampling Operation Summary of Stages in Sampling

Terms Description
Primary Sample The collection of one or
more units initially
taken from the total
population of the
sample
Reduced Sample A representative part of
the primary sample
obtained by a division
or reduction process
Composite Sample Mixtures formed by
combining primary
samples
Laboratory Sample The sample sent to or
Sampling Plan received by the
• Step-by-step procedure that ensures laboratory
uniformity of sample taken with the lot. Analytical Sample The portion prepared
from the laboratory
1. Intuitive Sampling Plan
sample from which the
- Based on incidental judgement or
portions for analysis are
previous experience taken
2. Statistical Sampling Plan Analytical Portion The quantity of sample
- Provides data for probability of the proper weight for
conclusions each analytical
3. Protocol Sampling Plan instrument
- Specified for decision-making
purposes Types of Samples
• Plan must answer: 1. Representative samples
a) What do we want to know? - parent material for characteristics under
b) Why do we need this information? inspection (homogenous,
c) What happens to the results? heterogenous, static or dynamic
d) What actions may follow? 2. Selective Samples
Types of Samples - selected because of certain
characteristics
1. According to Physical State 3. Random Samples
- Gas - Selected by random process
- Liquid - Random to eliminate on having bias
- Solid samples selection
2. According to Phase - Provide basis when it comes to
- Homogenous statistical interpretation of
- Heterogenous measurement on data
3. According to Sampling Operation a) Simple Random Sampling
- Primary sample - Equal chance of election
- Test sample b) Stratified Random sampling
- Laboratory sample - Division of groups
4. According to Sampling Plan c) Systematic Random Sampling
- Representative - Subsequent sample can be
- Selective taken according to the
- Random previous arrangement of
- Composite interval
4. Composite Sampling
- cause reduction
- two or more portions of selected
material are put together and you will
pick the sample to be tested
 Error and Sampling
Sampling and Analysis Operations
Designing your sampling plan
1. Definition of objectives of the measurement
3. Selection of Analytical Methods
4. Determination of Sampling Locations
5. Determination of Number of Increments
6. Determination of Sampling Methods
7. Selection of Methods for Sample
Preservation and Pretreatment
8. Preparation and Review of Final Plan
Approaches to Sampling
Systematic Sampling
- Increments are taken at predetermined
(programmed) intervals as defined by
sampling plan
Stratified Sampling
- Involved division of lot into groups then
taking material from each group
Statistical Sampling
- All particles or portion of the material should
have an equal probability of being present in
the sample taken
- The parameter being determined during the
analysis has a normal distribution in the
population
Coning & Quartering Method
Sampling Equipment
Hand Scoops
- for sampling solids with loose particles from
bags and from bulk
Thief (Drum Thief)
- a tube with a slit running its entire length,
with one end attached to a handle and the
other end with a shard cutting edge
- It is inserted into the solid mass or a container
of the solid with sufficient rotation
- It is used for solids with loose of compacted
particles
Probe
- A metal tube that is inserted vertically into
the bulk to retain a core of the sample
Riffler
- A mechanical device for dividing a sample
into two equal portions
Dipper
- For sampling from the surface of a liquid
system
Thief Sampler
- Involved a container which can be opened
mechanically from the other end
Sampling Bomb
- Use to sample gaseous samples
Drip Sampler
- Used to sample liquids in storage tanks with
flow tubes (ex. Bunker fuels, condensates
and gasoline)
Error and Sampling