1. What are significant figures?

 The minimum number of digits required to express a value in scientific

notation without loss of precision.

2. Rules for determining which digits are significant:

 1. All non-zero numbers are significant
 2. Zeros between non-zero numbers are significant
 3. Zeros to the right of the non-zero number and to the right of the
decimal point are significant
 3. Zeros before the non-zero numbers are not significant

3. What is experimental error?

 Ever measurement has some uncertainty, which is called experimental
error.
 Conclusions can be expressed with a high or low degree of confidence,
but never with complete certainty.
 Experimental error is the difference between the “true” value and the
measured value.
 Experimental error is classified as systemic, random, or blunder.

4. What is systematic error?

 Systematic error, also called determinate error, arises from a flaw in
equipment or the design of an experiment or personal errors.
 If you conduct the experiment in exactly the same manner, the error is
reproducible.
 In principle, systematic errors can be discovered and corrected,
although it may not be easy.

5. Ways to detect systematic error?

 Analyze a known sample, such as a certified reference material. Your
method should reproduce the known answer.
  Analyze a blank sample containing no analyte being sought. If you
observe a nonzero result, you method responds to more than you
intend. E.g.: different kind of blanks.
 Use different analytical methods to measure the same quantity. If
results do not agree, there is error in (or more) of the methods.
 Round robin method: different people in several laboratories analyze
identical samples by the same or different methods. Disagreement
beyond the estimated random error is systematic error.

6. What is Standard Reference Sample?

 The U.S. National Institute of Standards and Technology and national
standards laboratories in other countries sell certified reference
materials (called standard reference materials in the U.S.), such as
clinical and environmental standards and engineering materials that you
can use to test the accuracy of your analytical procedure.

7. What is Random error and types?

 Random error, also called indeterminate error, arises from uncontrolled
(and maybe uncontrollable) variables in the measurement. Random
error has an equal chance of being positive or negative.
 It is always present and cannot be corrected or eliminated, but it might
be reduced by a better experiment.
 Examples include: reading a scale on an instrument caused by the finite
thickness of the lines on the scale and electrical noise in an instrument.

8. What is precision?
 Precision describes the reproducibility of a result. If you measure a
quantity several times and the values agree closely with one another,
your measurement is precise. If the values vary widely, your
measurement is not precise.

9. What is accuracy?
  Accuracy describes how close a measured value is to the “true” value. If
a known standard is available, accuracy is how close your value is to the
known value.

10. What is the difference between absolute uncertainty and relative

uncertainty?
 Absolute uncertainty expresses the margin of uncertainty associated
with a measurement. If the estimated uncertainty in reading a calibrated
burette is ±0.02 mL, we say that ±0.02 mL is the absolute uncertainty
associated with the reading.
 Relative uncertainty compares the size of the absolute uncertainty with
the size of its associated measurement. The relative uncertainty of a
burette reading of 12.35±0.02 mL is a dimensionless quotient:

11. What is quality assurance?

 Quality assurance is what we do to get the right answer for our purpose.

12. Quality assurance process:

13. Specifications could include:

• sampling requirements

• Accuracy and precision

• Rate of false results

• Selectivity

• Sensitivity

• Acceptable blank values

• Recovery of fortification (spike recovery)

• Calibration checks

• Quality control samples

14. Explain sample requirements (Specifications #1):
 Quality assurance begins with sampling. We must collect representative
samples, and analyte must be preserved after samples are collected. If
our sample is not representative or if analyte is lost after collection, then
even the most accurate analysis is meaningless.

15. Explain accuracy and precision (Specification #2):

 Within practical restraints, (cost, time, and limited amounts of material),
what level of accuracy and precision will satisfy the use objectives?

16. Explain acceptable rate of false results (Specification #3):

 A false positive says that the concentration exceeds the legal limit when,
in fact, the concentration is below the limit. A false negative says that
the concentration is below the limit when it is actually above the limit.

17. Explain selectivity (Specification #4):

 Selectivity means being able to distinguish analyte from other species in
the sample (avoiding interference).
18. Explain sensitivity (Specification #5):
 Sensitivity is the capability of responding reliably and measurably to
changes in analyte concentration.
 The detection limit of an analytical method must be lower than the
concentrations to be measured.
19. Explain acceptable blank values (Specification #6):
 Blanks account for:
– Interference by other species in the sample
– Traces of analyte found in reagents used for sample preservation,
preparation, and analysis
– Frequent measurements of blanks detect whether analyte from
previous samples is carried into subsequent analyses by adhering to
vessels or instruments.
 Three types – method, reagent, and field blanks.

20. Explain the types of blanks:

 1. A method blank is a sample containing all components except analyte,
and is taken through all analytical steps. We subtract the response ofthe
method blank from the response of a real sample prior to calculating the
quantity of analyte in the sample.
 2. A reagent blank is similar to a method blank, but it has not been
subjected to all sample preparation steps.
 3. A field blank indicates if analyte is inadvertently picked up by
exposure to field conditions.

21. Explain recovery of fortification (spike recovery) (Specification #7):

 Sometimes, response to analyte can be decreased or increased by
something else in the sample.
 Matrix refers to everything in the sample other than analyte.
 A spike, also called a fortification, is a known quantity of analyte added
to a sample to test whether the response to the spike is the same as
that expected from the calibration curve.
 Spiked samples are analyzed in the same manner as unknowns.
[Link] calibration check (Specification #8):
 In a calibration check, we analyze solutions with known concentrations
of analyte.
 A specification might, for example, call for one calibration check for
every 10 samples.
 Calibration check solutions should be different from the ones used to
prepare the original calibration curve.
 This practice helps verify that the initial calibration standards were
made properly.

[Link] quality control (Specification #9):

 Performance test samples (also called quality control samples or blind
samples) are a quality control measure to help eliminate bias
introduced by an analyst who knows the concentration ofthe calibration
check sample
 These samples of known composition are provided to the analyst as
unknowns.

24. What is standard operating procedure?

 Written standard operating procedures (SOP) must be followed
rigorously to avoid inadvertent changes in procedure that could affect
the outcome.
 It is implicit that everyone follows the standard operating procedures.
  Adhering to these procedures guards against the normal human desire
to take shortcuts based on assumptions that could be false.

25. Explain Control charts used in (Assessment):

 A control chart is a visual representation of confidence intervals for
measurements having a Gaussian distribution.
 Warn us when a property being monitored strays dangerously far from
an intended target value.
 Can be used to monitor accuracy, precision, or instrument performance
as a function of time.
[Link] Method Validation:
 Method validation is the process of proving that an analytical method is
acceptable for its intended purpose.
 In validating a method, we typically demonstrate that requirements are
met for
- specificity,
- linearity,
- accuracy,
- precision,
- range,
- limit of detection,
- limit of quantitation,
- robustness

27. Explain Selectivity (Method Validation #1):

 Selectivity is extent to which a method can distinguish analyte from
everything else in the sample.
 A method is specific if the selectivity is absolute, such that there are no
interferences.

[Link] is linearity? (Method Variation #2):

  Linearity measures how well a calibration curve follows a straight line,
showing that response is proportional to the quantity of analyte.
 Linearity is usually measured by the square of the correlation coefficient
for the calibration curve.
29. Accuracy (Method Variation #3):
 Accuracy is “nearness to the truth.” Ways to demonstrate accuracy
include
 1. Analyze a certified reference material in a matrix similar to that of
your unknown.
 2. Compare results from two or more different analytical methods. They
should agree within their expected precision.
 3. Analyze a blank sample spiked with a known addition of analyte. The
matrix must be the same as in your unknown. Spiking is the most
common method to evaluate accuracy because reference materials are
not usually available and a second analytical method may not be readily
available. Spiking with a small volume of concentrated analyte ensures
that the matrix remains nearly constant.
 4. If you cannot prepare a blank with the same matrix as the unknown,
standard additions of analyte to the unknown should be used. Spiking is
the most common method to evaluate accuracy because reference
materials are not usually available and a second analytical method may
not be readily available. Spiking with a small volume of concentrated
analyte ensures that the matrix remains nearly constant.

[Link] (Method Variation #4):

 Precision is how well replicate measurements agree with one another,
usually expressed as a standard deviation, a standard uncertainty
(standard deviation of the mean), or a confidence interval.
 Two broad categories of precision are repeatability and reproducibility.
Repeatability describes the spread in results when one person uses one
procedure to analyze the same sample by the same method multiple
times. Reproducibility describes the spread in results when different
 people in different labs using different instruments each try to follow
the same procedure.
 Types of precision include instrument precision, intra-assay precision,
intermediate precision, and, most generally, interlaboratory precision.
31. Range (Method Variation #5):
 Range is the concentration interval over which linearity, accuracy, and
precision are all acceptable.

[Link] detection limit and quantitation (Method Variation#6,7):

 The detection limit (LOD) is usually taken as three times the standard
deviation of the blank.
 The lower limit of quantitation (LOQ) is 10 times the standard deviation
of the blank.
 The reporting limit is the concentration, below which regulations say
that a given analyte is reported as “not detected,” which does not mean
that analyte is not observed. It means that analyte is below a prescribed
level.

[Link] between standard addition and Internal standard:

STANDARD ADDITIION:
 A standard addition is a known quantity of analyte added to an
unknown to increase the concentration of analyte. Standard additions
are especially useful when matrix effects are important.
 From the increase in signal, we deduce how much analyte was in the
original unknown.

INTERNAL STANDARD:
 An internal standard is a known amount of a compound — different
from analyte — that is added to the unknown.
 Signal from analyte is compared with signal from the internal standard
to find out how much analyte is present.
  Internal standards are useful when the quantity of sample analyzed is
not reproducible, when instrument response varies from run to run, or
when sample losses occur in sample preparation.
 The response factor F is the relative response to analyte and standard

34. How to prepare a solution?

 To prepare a solution with a desired molarity from a pure solid or liquid,
we weigh out the correct mass of reagent and dissolve it in a volumetric
flask with distilled or deionized water.

[Link] Dilution:
 Dilute solutions can be prepared from concentrated solutions.
 A volume of the concentrated solution is transferred to a fresh vessel
and diluted to the desired final volume.
 The number of moles of reagent in V liters containing M moles per liter
is the product M.V.

[Link] is Stoichiometry?
 Stoichiometry is the calculation of quantities of substances involved in a
chemical reaction. It is derived from the Greek stoicheion (simplest
components) and metiri (to measure)