Basic Analytical Tools (CHM112)

Dr. Kathlia A.
De Castro-Cruz
Analytical Chemistry 1
Basic Analytical Tools
kadecastro-cruz 1
What is Analytical Chemistry?
! It is what analytical chemist do
" Analytical chemists work to improve the ability
of all chemists to make meaningful
measurements.
! Often described as the area of chemistry
responsible for characterizing the composition
of matter, both qualitatively (what is present)
and quantitatively (how much is present)
misleading definition
kadecastro-cruz 2
! The craft of analytical chemistry is not in
performing a routine analysis on a routine
sample (chemical analysis), but in improving
established methods, extending existing
methods to new types of samples, and
developing new methods for measuring
chemical phenomena
! The science of inventing and applying the
concepts, principles, and strategies for
measuring the characteristics of chemical
systems and species
kadecastro-cruz 3
! Typical problems on which analytical chemists
work include
" qualitative analyses (what is present?),
" quantitative analyses (how much is present?),
" characterization analyses (what are the
materials chemical and physical properties?),
" and fundamental analyses (how does this
method work and how can it be improved?)
kadecastro-cruz 4
Classification of Analysis
! Based on goal of analysis
" Qualitative analysis an analysis carried
out to determine only the identity of a pure
analyte, the identity of an analyte in a
matrix, or the identity of several or all
components of a mixture
" Quantitative analysis the analysis of a
material for how much of one or more
components is present
kadecastro-cruz 5
! Based on nature of method used
" Physical property analysis involves no
chemical reactions and at times relatively
simple devices (although possibly
computerized) to facilitate the measurement.
Physical properties are especially useful for
identification, but may also be useful for
quantitative analysis in cases where the value
of a property, such as specific gravity or
refractive index, varies with the quantity of an
analyte in a mixture.
kadecastro-cruz 6
! Based on nature of method used
" Wet chemical analysis - involves chemical
reactions or classical reaction stoichiometry,
but no electronic instrumentation beyond a
weighing device
" Instrumental analysis can also involve
chemical reactions, but it always involves
modern sophisticated electronic
instrumentation. Instrumental analysis
techniques are high-tech techniques, often
utilizing complex hardware and software
kadecastro-cruz 7
Calculate
and report
the results
(5)
Obtain
Sample
(1)
Prepare
the sample
(2)
Work
the data
(4)
Carry out
the analysis
Method
(3)
General Analytical
Strategy
Analytical Strategy
Basic Analytical Tools kadecastro-cruz 8
Calculate
and report
the results
(5)
Obtain
Sample
(1)
Prepare
the sample
(2)
Work
the data
(4)
Carry out
the analysis
Method
(3)
General Analytical
Strategy
Analytical Strategy
The sample must
be representative
of the bulk
system; its
integrity must be
maintained; and
the chain of
custody must be
documented.
A portion of the sample
is prepared for the
analysis by weighing it
(or measuring its
volume) and carrying
out certain physical
and/or chemical
processes, such as
drying, dissolving, etc.
Obtain weight or volume data on the prepared sample
Prepare reference standards of the analyte or substances
with which the analyte will react.
Standardize solutions or calibrate equipment
Obtain the required data for the sample
A final calculation may be
necessary to obtain the
desired results.
This requires
calculations and/
or the plotting of a
calibration curve
from which the
desired results
can be derived.
Statistics are
usually involved
Basic Analytical Tools kadecastro-cruz 9
10 Basic Analytical Tools kadecastro-cruz
Sampling
! The process of obtaining samples for analyses
" Samples must possess all the characteristics
of the entire bulk system with respect to the
analyte and the analyte concentration in the
system (representative sample)
! Plays a crucial role in the quality and success
of an analysis
Sampling
! Samples maybe
" Bulk sample
" Primary sample
" Secondary sample
" Sub sample
" Laboratory sample
" Test sample
Sampling: Solid
! Sample preparations
" Particle size reduction
# Maybe crushing, milling, grinding or
pulverizing
" Sample homogenization and division
" Solid-liquid extraction
" Total dissolution
# May use acids
Sampling: Solid
! Total Dissolution
Name Formula Description Example Uses
Water H
2
O clear, colorless liquid with low
vapor pressure, highly polar
Dissolving polar
and ionic
compounds
Hydrochloric
acid
HCl Commercially available
concentrated solution is 38% (12
M) HCl; evolves pungent fumes
and must be handled in fume
hood
Dissolving some
metals and metal
ores
Sulfuric acid H
2
SO
4
Commercially available
concentrated solution is 96% (18
M) H
2
SO
4
; a dense, syrupy liquid;
reacts on contact with skin and
clothing; evolves much heat
when mixed with water
Organic samples,
such as for
Kjeldahl analysis;
also oxides of Al
and Ti
Sampling: Solid
! Total Dissolution
Nitric acid HNO
3
Commercially available
concentrated solution is 70%
(16 M) HNO
3
; reacts with
clothing and skin (turns skin
yellow); evolves thick brown
and white fumes when in
contact with most metals
Dissolving noble
metals (e.g.,
copper and silver)
and also some
organic samples
Hydrofluoric
acid
HF Commercially available
concentrated acid is 50% (26
M) HF; must be stored in
plastic containers, since it
attacks glass; very damaging
to skin
Dissolving silica-
based materials
and stainless steel
Sampling: Solid
! Total Dissolution
Perchloric acid HClO
4
Commercially
available
concentrated
solution is 72% (12
M) HClO
4
Dissolving difficult
organic samples and
stable metal alloys
Aqua regia A mixture of
concentrated HNO
3

and HCl in the ratio
of 1:3 HNO
3
:HCl

Dissolving highly
unreactive metals,
such as gold
Sampling: Solid
! Sample preparations
" Fusion
# dissolving of a sample using a molten
inorganic salt, generally called a flux, as the
solvent.
# This flux dissolves the sample and, upon
cooling, results in a solid mass that is then
soluble in a liquid reagent.
Sampling: Liquids and Extracts
! Extraction from Liquid solutions
" Maybe liquid-liquid, solid phase or purge
and trap
! Dilution and Concentration
! Derivatization
" To preserve the sample that are unstable
Reagents for Sample Preparation
! A reagent is a substance used in a chemical
reaction in an analytical laboratory because of its
specific applicability to a given system or
procedure.
" Primary standard: A specially manufactured
analytical reagent of exceptional purity for
standardizing solutions and preparing reference
standards.
" ACS certified: A reagent that meets or exceeds the
specifications of purity put forth by the American
Chemical Society. The certificate of analysis is on
the label.
" Certified reagent: A reagent that meets the
standards of purity established by the
manufacturer. The certificate of analysis is on
the label.
" USP/NF: Reagents that meet the purity
requirements of the U.S. Pharmacopeia (USP)
and the National Formulary (NF). Generally of
interest to the pharmaceutical profession,
these specifications may not be adequate for
reagent use.
" Spectro grade or spectranalyzed: Solvents of
suitable purity for use in spectrophotometric
procedures. A certificate of analysis is on the
label.
" High-performance liquid chromatography
(HPLC) grade: Solvents of suitable purity for
use in liquid chromatography procedures.
" Practical: Chemicals of sufficiently high quality
to be suitable for use in some syntheses.
Organic chemicals of practical grade may
contain small amounts of intermediates,
isomers, or homologs.
" Technical: Chemicals of reasonable purity for
applications that have no official standard for
purity.
Interferences
! Substance that affects the analytical signal or
the background
! Foreign species that either attenuate the signal
from the analyte or produce a signal that is
indistinguishable from that of the analyte
! Also known as interferent
Interferences
! Method of eliminating interferences in chemical
analysis
Method Basis of Method
Masking Immobilization of interferent as a
nonreactive complex
Mechanical Separation
Precipitation
and filtration
Difference in solubility of compounds
formed
Distillation Difference in volatility of compounds
Extraction Difference in solubility in two
immiscible liquids
Interferences
! Method of eliminating interferences in chemical
analysis
Method Basis of Method
Ion exchange difference in stability of reactants
with an ion-exchange resin
Chromatography Difference in rate of movement of a
solute through a stationary phase
Electrophoresis Difference in migration rate in an
electrical field
Interferences Elimination
! Masking
" Addition of reagent to the solution of the
sample to immobilize or chemically bind, the
interferent as a complex that no longer
contributes to or attenuates the signal from
the analyte
# Masking agent a reagent that chemically binds
an interferent as a complex & prevents it from
causing errors in an analysis
! Masking
Masking Agent
Metals that can be
masked
Metals that
could not be
masked
F
-
Al
+3
, Fe
3+
, Ti
4+
, Be
4+

CN
-
Cd
2+
, Zn
2+
, Hg
2+
, Co
2+
,
Cu
+
, Ag
+
, Ni
2+
, Pd
2+
,
Pt
2+
, Fe
2+
, Fe
3+

Mg
2+
, Ca
2+
,
Mn
2+
, Pb
2+

Triethanolamine Al
3+
, Fe
3+
, Mn
2+

2,3-dimercapto-1-
propanol
Bi
3+
, Cd
2+
, Cu
2+
, Hg
2+
,
Pb
2+

! Demasking
" Releases metal ion from a masking agent
# Example: cyanide complexes can be
demasked using formaldehyde
! Separation by Precipitation
" Requires large solubility differences between
the analyte and the possible interferences
" Needs to consider factors affecting
precipitation such as coprecipitation
phenomena
" Could be
# Separations Based on Control of Acidity
# Sulfide Separations
! Separation by Precipitation
" Could be
# Separations by other Inorganic precipitants
# Separations by Organic Precipitants
# Separation of Species Present in Trace Amounts
by Precipitation
# Separation by Electrolytic Precipitation
# Salt-induced precipitation of Proteins

! Separation based on control acidity
" Separations based on pH control
" Three categories
# Those made in relatively concentrated solutions
of strong acids

# Those made in buffered solutions at intermediate
pH values
# Those made in concentrated solutions of sodium
or potassium hydroxide
! Separation based on control acidity
! Sulfide Separations
! Separation by other inorganic precipitants
" Phosphate, carbonate, and oxalate ions are
often employed as precipitants for cations
(nonselective)
" Chloride and sulfate
# Highly selective

! Separation by organic precipitants
" Dimethylglyoxime (has remarkable selectivity
in forming precipitates)
" 8-hydroxyquinoline
! Separation of Species Present in Trace Amounts
by Precipitation
" Used in isolation species present in
microgram quantities
" Collector
# Used to remove trace constituents from solution
# Example: Al
2
O
3
as collector of trace amounts of
titanium/CS for collection of traces of Zn and Pb

! Separation by Electrolytic Precipitation
" The more easily reduced species, either the
wanted or the unwanted component of the
sample is isolated as a separate phase
! Salt-induced Precipitation of Proteins
" Addition of high concentration of salt (salting
out)
! Separation of species by distillation
" Distillation is widely used to separate volatile
analytes from nonvolatile interferents
" Maybe
# Simple
# Fractional
# Steam
! Separation by extraction
" The extent to which solutes both inorganic
and organic, distribute themselves between
two immiscible liquids is used to accomplish
separation
" Governed by Distribution Law
" Frequently used in separating inorganic
species
! Separation by extraction
! Separation by Ion Exchange
" A process by which ions held in porous,
essentially insoluble solid are exchanged for
ions in a solution that is brought into contact
with the solid
" Used to eliminate ions that would otherwise
interfere with an analysis
Numbers in Analytical Chemistry
! Fundamental Units of Measurements
" Measurements usually consist of a unit and a
number expressing the quantity of that unit.
# SI units after the Systme International
dUnits are the internationally agreed on units
for measurements
# Standards of length, mass, and time are the
meter (m), kilogram (kg), and second (s),
respectively. Temperature is measured in
kelvins (K), amount of substance in moles
(mol), and electric current in amperes (A).
kadecastro-cruz 41
! Fundamental Units of Measurements
" Common prefixes used for exponential
notation
kadecastro-cruz 42
! Significant Figures
" The digits in a measured quantity, including all
digits known exactly and one digit (the last)
whose quantity is uncertain.
" reflection of a measurements uncertainty
" It is equal to the number of digits in the
measurement, with the exception that a zero
(0) used to fix the location of a decimal point is
not considered significant.
kadecastro-cruz 43
! Rules in Significant Figures
" For measurements using logarithms, such as
pH, the number of significant figures is equal
to the number of digits to the right of the
decimal, including all zeros. Digits to the left of
the decimal are not included as significant
figures since they only indicate the power of 10.
# Example: pH = 2.45 (has 2SF)
" Exact numbers, such as the stoichiometric
coefficients in a chemical formula or reaction,
and unit conversion factors, have an infinite
number of significant figures.
kadecastro-cruz 44
! Rules in Significant Figures
" Mathematical operations involving addition
and subtraction are carried out to the last
digit that is significant for all numbers
included in the calculation.
# Example: the sum of 135.621, 0.33, and 21.2163
is 157.17
" When multiplying and dividing, the general
rule is that the answer contains the same
number of significant figures as that number in
the calculation having the fewest significant
figures.
kadecastro-cruz 45
! Units of expressing concentration
" Concentration is a general measurement
unit stating the amount of solute present in
a known amount of solution
" Molarity - The number of moles of solute per
liter of solution (M)
" Formality The number of moles of solute,
regardless of chemical form, per liter of
solution (F)
kadecastro-cruz 46
" Normality The number of equivalents of
solute per liter of solution (N).
# The number of equivalents, n, is based on a
reaction unit, which is that part of a chemical
species involved in a reaction
$ n for salt = charge
$ n for acid = no of replaceable H
$ n for base = no of replaceable IH
$ n for redox = no of electrons involved
# Relationship between Molarity and Normality
is: N = n x M
kadecastro-cruz 47
" Molality The number of moles of solute per
kilogram of solvent (m).
" Weight percent Grams of solute per 100 g of
solution (% w/w).
" Volume percent Milliliters of solute per 100
mL of solution (% v/v).
" Weight-to-volume percent Grams of solute
per 100 mL of solution (% w/v).
kadecastro-cruz 48
" parts per million Micrograms of solute per
gram of solution; for aqueous solutions the
units are often expressed as milligrams of
solute per liter of solution (ppm).
" parts per billion Nanograms of solute per
gram of solution; for aqueous solutions the
units are often expressed as micrograms of
solute per liter of solution (ppb).
" p functions expressing concentration that
contains span many orders of magnitude
kadecastro-cruz 49
kadecastro-cruz 50
! Sample Problems
" Calculate the formula mass of CaSO
4
. What
is the molarity of CaSO
4
in a solution
containing 1.2 g CaSO
4
in a volume of 50
mL? How many grams of CaSO
4
are in 50
mL of 0.086M CaSO
4
?
kadecastro-cruz 51
Answers: 136.14 g/mol
0.18 M, 0.59 g
! Sample Problems
" Calculate the molarity and molality of 49.0
wt% HF. Density of HF = 1.30 g/mL
kadecastro-cruz 52
Answers: 31.8 M, 48.0 m
! Sample Problems
" Normal alkanes are hydrocarbons with the
formula CnH2n+2. Plants selectively
synthesize alkanes with an odd number of
carbons. The concentration of C
29
H
60
in
summer rain water collected is Hannove,
Germany is 34 ppb. Find the molarity of
C
29
H
60
and express the answer using prefix.
How many ppm of C
29
H
60
are in 23!M
C
29
H
60
?
kadecastro-cruz 53
Answers: 83 nM, 9.4 ppm
! Sample Problems
" Copper (II) sulpfate pentahydrate, CuSO
4

5H
2
0, has 5 moles of H
2
O for each mole of
CuSO
4
cryatal. How many grams of CuSO
4

5H
2
0 should be dissolved in a volume of
500.0 mL to make 8.00mM Cu
2+
?
kadecastro-cruz 54
Answers: 0.999 g
! Sample Problems
" The molarity of concentrated HCl
purchased for laboratory used is
approximately 12.1M How many milliliters
of this reagent should be diluted to prepare
1.00oL of 0.100M HCl solution.
kadecastro-cruz 55
Answers: 8.26 mL
! Sample Problems
" In a gravimetric analysis, we need enough
product to weigh accurately. Each table
provide ~15 mg iron. How many tablets
should we analyze to provide 0.25 g of
Fe
2
O
3
product?
kadecastro-cruz 56
Answers: 12 Tablets
Errors in Analytical Measurements
! Classification of errors
" Systematic errors (determinate errors)
generally arise from determinate or identifiable
sources causing measured values to differ from
a true or accepted value. These errors can be
avoided and the magnitude could be measured.
# Operational and personal errors these are
due to factors for which the individual analysts
is responsible and are not connected with the
method or procedure
kadecastro-cruz 57
! Classification of errors
# Instrumental and reagent errors these arise
from the faulty construction of balances, the
use of uncalibrated or improperly calibrated
weights, graduated glassware and other
instruments
# Errors of method originate from incorrect
sampling and from incompleteness of a
reaction
# Additive and proportional errors
kadecastro-cruz 58
! Measurement of errors
" Accumulated errors - Errors are associated
with every measurement made in an analytical
procedure, and these will be aggregated in the
final calculated result. The overall error for
determinate error maybe calculated using
either of the following expression:
# where only a linear combination of individual
measurements is required to compute the
result, the overall absolute determinate error,
E
T
, is given by:
E
T
=E
1
+E
2
+E
3
+.......
kadecastro-cruz 59
! Measurement of errors
E
1
and E
2
etc., being the absolute determinate
errors in the individual measurements taking
sign into account
# where a multiplicative expression is required
to compute the result, the overall relative
determinate error, E
TR
, is given by
E
TR
=E
1R
+E
2R
+E
3R
+.....

E
1R
and E
2R
etc., being the relative determinate
errors in the individual measurements taking
sign into account.
kadecastro-cruz 60
Accuracy and Precision
! Accuracy
" The closeness of an experimental measurement
or result to the true or accepted value.
" It is generally the more important
characteristic of quantitative data to be
assessed, although consistency, as measured by
precision, is of particular concern in some
circumstances.
kadecastro-cruz 61
! Precision
" The closeness of agreement between
replicated measurements or results
obtained under the same prescribed
conditions.
" Can be assessed in several ways.
# Spread or range (i.e. the difference between
the highest and lowest value) is sometimes used
# Standard deviation of the data popularly
used.
kadecastro-cruz 62
! Precision
" Commonly divided into two categories:
# Repeatability - the precision obtained when
all measurements are made by the same
analyst during a single period of laboratory
work, using the same solutions and
equipment.
# Reproducibility - the precision obtained
under any other set of conditions, including
that between analysts, or between
laboratory sessions for a single analyst.
kadecastro-cruz 63
! Precision vs Accuracy
" Commonly divided into two categories:
kadecastro-cruz 64

Introduction to Analytical Science

13

1.7.5 Statistical Control

A given device, procedure, process, or method is usually said to be in

statistical control

if numerical
values derived from it on a regular basis (such as daily) are consistently within 2 standard deviations
from the established mean, or the most desirable value. As we learned in Section 1.7.3, such numerical
values occur statistically 95.5% of the time. Thus if, say, two or more consecutive values differ from the
established value by more than 2 standard deviations, a problem is indicated because this should happen
only 4.5% of the time, or once in roughly every 20 events, and is not expected two or more times
consecutively. The device, procedure, process, or method would be considered out of statistical control,
indicating that an evaluation is in order.
Similarly, if just one individual numerical value differs from the established mean by more than 3
standard deviations, a problem is also indicated because, as we also saw in Section 1.7.3, this should only
occur 0.3% of the time, or once in every 333 events. Again, an evaluation is in order.
Analytical laboratories, especially quality assurance laboratories, will often maintain graphical records
of statistical control so that scientists and technicians can note the history of the device, procedure,
process, or method at a glance. The graphical record is called a

control chart

and is maintained on a
regular basis, such as daily. It is a graph of the numerical value on the y-axis vs. the date on the x-axis.
The chart is characterized by ve horizontal lines designating the ve numerical values that are important
for statistical control. One is the value that is 3 standard deviations from the most desirable value on the
positive side. Another is the value that is 3 standard deviations from the most desirable value on the
negative side. These represent those values that are expected to occur only less than 0.3% of the time.
These two numerical values are called the action limits because one point outside these limits is cause
for action to be taken.
Additionally, two other horizontal lines are drawn at the values that are 2 standard deviations from
the most desirable value, one on the positive side and one on the negative side. These represent those
values that are expected to occur only 4.5% of the time. The fth horizontal line is the desirable line
itself. See Figure 1.5.

FIGURE 1.4 Illustration of precision and accuracy.
Neither precise
nor accurate
Precise but
not accurate
Accurate
and precise
L1519_Frame_C01.fm Page 13 Monday, November 3, 2003 11:27 AM
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13



statistical control

if numerical

control chart


Neither precise
nor accurate
Precise but
not accurate
Accurate
and precise


13



statistical control

if numerical

control chart


Neither precise
nor accurate
Precise but
not accurate
Accurate
and precise
Statistics and Statistical Analysis
! Mean, arithmetic mean or average
" obtained by dividing the sum of replicate
measurements by the number of
measurements in the set:
kadecastro-cruz 65
!
x =
x
i
i =1
N
"
N
where x
i
represents individual values of x
making up a set of N replicate measurements
! Median
" the middle result when replicate data are
arranged in order of size
! Range
" the difference between the largest and
smallest values in the data set.
kadecastro-cruz 66
!
w = x
l arg est
" x
smallest
! Deviation, d
" determines how far the measured value
deviates from the mean.
! Estimated Standard deviation, s
" measure of the dispersion of data around the
mean
kadecastro-cruz 67
!
d = x " x
i
!
s =
(d
1
2
+ d
2
2
+ d
3
2
+ ...
n "1
where n is the number of measurements and n-1 is the
degrees of freedom
! Standard Deviation, s
" the smaller it is numerically, the more precise the
data (the more the measurements are bunched
around the mean)
" For an infinite number of measurements (where
the mean is m), the standard deviation is
symbolized as s (Greek letter sigma) and is known
as the population standard deviation. 30 or
more measurements approximate an infinite
number of measurements.
kadecastro-cruz 68
!
" =
(x
i
# )
2
i =1
N
$
N
! Variance
" The square of the standard deviation, !
2
, or
estimated standard deviation, !
2
, is used in a
number of statistical computations and tests, such
as for calculating accumulated (propagated) errors
or when comparing the precisions of two sets of
data.
kadecastro-cruz 69
! Relative Standard Deviation
" Relates the standard deviation to the value of the
mean and represents a practical and popular
expression of data quality. It is calculated by
dividing the standard deviation by the mean and
then multiplying by 100 or 1000:
kadecastro-cruz 70
!
RSD =
s
x
relative % standard deviation = RSD x 100
relative parts per thousand standard deviation = RSD x 1000
! Normal Distribution
Curve
" For an infinite data
set (in which the
symbols and !
apply), a plot of
frequency of
occurrence vs. the
measurement value
yields a smooth bell-
shaped curve.
kadecastro-cruz 71
between-runs variability. It may also be important to establish the precision of
individual steps in an analysis.
This is the most widely used measure of precision and is a parameter of the
normal error or Gaussian curve (Topic B1, Fig. 4). Figure 2 shows two curves for
the frequency distribution of two theoretical sets of data, each having an innite
number of values and known as a statistical population.
Standard
deviation
28 Section B Assessment of data
Deviation from mean
F
r
e
q
u
e
n
c
y

o
f

o
c
c
u
r
r
e
n
c
e
o
f

e
a
c
h

d
e
v
i
a
t
i
o
n
sd = s
2
sd = s
1
s
1
> s
2
m +
Fig. 2. Normal error or Gaussian curves for the frequency distributions of two statistical
populations with differing spreads.
The maximum in each curve corresponds to the population mean, which for
these examples has the same value, m. However, the spread of values for the
two sets is quite different, and this is reected in the half-widths of the two
curves at the points of inection, which, by denition, is the population stan-
dard deviation, s. As s
2
is much less than s
1
, the precision of the second set is
much better than that of the rst. The abscissa scale can be calibrated in
absolute units or, more commonly, as positive and negative deviations from the
mean, m.
In general, the smaller the spread of values or deviations, the smaller the
value of s and hence the better the precision. In practice, the true values of m
and s can never be known because they relate to a population of innite size.
However, an assumption is made that a small number of experimental values or
a statistical sample drawn from a statistical population is also distributed
normally or approximately so. The experimental mean, x
_
, of a set of values x
1
,
x
2
, x
3
,.x
n
is therefore considered to be an estimate of the true or population
mean, m, and the experimental standard deviation, s, is an estimate of the true
or population standard deviation, s.
A useful property of the normal error curve is that, regardless of the magni-
tude of m and s, the area under the curve within dened limits on either side of
m (usually expressed in multiples of s) is a constant proportion of the total
area. Expressed as a percentage of the total area, this indicates that a particular
percentage of the population will be found between those limits.
Thus, approximately 68% of the area, and therefore of the population, will be
! Uncertainty - the range of possible values for
a measurement
! Confidence Interval - the range of values
around an experimental result within which
the true or accepted value is expected to lie
with a defined level of probability.
kadecastro-cruz 72
! Confidence Interval
" Known standard deviation:
kadecastro-cruz 73
!
CL() = x
z"
N
where z is a statistical factor related
to the probability level required
Confidence
Level%
z
Confidene Level, %

z
50 0.67 95.4 2.00
68 1.00 99 2.58
80 1.29 99.7 3.00
90 1.64 99.9 3.29
95 1.96
! Confidence Interval
" Using estimated standard deviation:
kadecastro-cruz 74
where t is a statistical factor related to the probability level
but in addition determined by the number of degrees of
freedom for the set of data, i.e. one less than the number of
results.
!
CL() = x
ts
N
kadecastro-cruz 75
Degrees of
Freedom
Factor for Confidence Interval
80% 90% 95% 99% 99.9%
1 3.08 6.31 12.7 63.7 637
2 1.89 2.92 4.30 9.92 31.6
3 1.64 2.35 3.18 5.84 12.9
4 1.53 2.13 2.78 4.60 8.60
5 1.48 2.02 2.57 4.03 6.86
6 1.44 1.94 2.45 3.71 5.96
7 1.42 1.90 2.36 3.50 5.40
8 1.40 1.86 2.31 3.36 5.04
9 1.38 1.83 2.26 3.25 4.78
10 1.37 1.81 2.23 3.17 4.59
11 1.36 1.80 2.20 3.11 4.44
12 1.36 1.78 2.18 3.06 4.32
13 1.35 1.77 2.16 3.01 4.22
14 1.34 1.76 2.14 2.98 4.14
! 1.29 1.64 1.96 2.58 3.29
! Standard deviation of computed results
kadecastro-cruz 76
! t Test
" This is used to compare one set of
measurements with another to decide whether
or not they are the same.
" Three cases:
# Case 1. Comparing a Measured Result with a
Known Value
kadecastro-cruz 77 !
t
calculated
=
x " known value
s
n
If t
calculated
> t
table
at 95% confidence level, the two results
are considered to be different.
! t Test
# Case 2. Comparing Replicate Measurements
(Use to decide whether two sets of replicate
measurements give the same or different
results )
$ For two sets of data consisting of n1 and n2
measurements:

kadecastro-cruz 78
!
t
calculated
=
x
1
" x
2
s
pooled
n
1
n
2
n
1
+ n
2
s
pooled
=
s
1
2
(n
1
"1) + s
2
2
(n
2
"1)
n
1
+ n
2
" 2
If t
calculated
> t
table
at
95% confidence
level, the two results
are considered to be
different.
! t Test
# Case 2. Comparing Replicate Measurements
$ If the population for both series of
measurement is different:

kadecastro-cruz 79
!
t
calculated
=
x
1
" x
2
s
1
2
n
1
+
s
2
2
n
2
!
Degrees of freedom =
s
1
2
n
1
+
s
2
2
n
2
"
#
$
%
&
'
2
s
1
2
n
1
"
#
$
%
&
'
2
n
1
+1
+
s
2
2
n
2
"
#
$
%
&
'
2
n
2
+1
"
#
$
$
$
$
%
&
'
'
'
'
(
)
*
*
*
*
*
+
*
*
*
*
*
,
-
*
*
*
*
*
.
*
*
*
*
*
/ 2
! t Test
# Case 3. Comparing Individual Differences (If
two different methods were used to make
single measurements on several different
samples, are they different?)

kadecastro-cruz 80
!
t
calculated
=
d
s
d
n
s
d
=
d
i
" d
( )
#
2
n "1
If t
calculated
> t
table
at 95% confidence level, the two results are
considered to be different.
! F Test
# Tells whether two standard deviations are
significantly different from each other

kadecastro-cruz 81
!
F
calculated
=
s
1
2
s
2
2
If F
calculated
> F
table
(95%), the standard deviation are
significantly different from each other.
! Q Test
# Use to help decide whether to retain or discard
questionable datum.

kadecastro-cruz 82
!
Q
calculated
=
gap
range
range is the total spread of the data
gap is the difference between the questionable point and
the nearest value
If Q
calculated
> Q
table
, the questionable
point should be discarded
! Q Test
# Values of Q for rejecting data

kadecastro-cruz 83
Q (90% confidence)
Number of
Observations
0.76 4
0.64 5
0.56 6
0.51 7
0.47 8
0.44 9
0.41 10
References
" Kenkel, J. (2003). Analytical Chemistry for
Technicians, 3
rd
ed. CRC Press, US.
" Harvey, D. (2000). Modern Analytical
Chemistry, McGraw-Hill, US, 104-134.
" Harris, D. (2007). Quantitative Chemical
Analysis, 8
th
ed., Freeman, NY.
kadecastro-cruz 84

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