ANALYTICAL

CHEMISTRY
STATISTICS
• Accuracy is a measure of how closely the result of
an experiment agrees with the expected result.
• The difference between the obtained result and the
expected result is usually divided by the expected
result and reported as a percent relative error.
𝑜𝑏𝑡𝑎𝑖𝑛𝑒𝑑 𝑟𝑒𝑠𝑢𝑙𝑡 −𝑒𝑥𝑝𝑒𝑐𝑡𝑒𝑑 𝑟𝑒𝑠𝑢𝑙𝑡
% 𝐸𝑟𝑟𝑜𝑟 = × 100
𝑒𝑥𝑝𝑒𝑐𝑡𝑒𝑑 𝑟𝑒𝑠𝑢𝑙𝑡𝑠
STATISTICS
• Precision is defined as the degree of agreement
between replicate measurements of the same
quantity.
• i.e. it is the repeatability of a result.
• Good precision does not assure good accuracy.
• This would be the case, for example, if there were a
systematic error in the analysis.
• A weight used to measure each of the samples may
be in error.
TYPES OF ERRORS
• Determinate errors or systematic errors are those
that are determinable and that presumably can be
either avoided or corrected .
• They may be constant as in the case of an
uncalibrated weight that is used in all weighings
COMMON DETERMINATE ERRORS
Instrumental errors
• These include faulty equipment, uncalibrated weights and
uncalibrated glassware.
Operative errors
• These include personal errors, and can be reduced by
experience and care of the analyst in the physical
manipulations involved.
• Operations in which these errors can occur include transfer
of solutions, effervescence and “bumping” during sample
dissolution, incomplete drying of samples and so on.
• These are difficult to correct for.
• Other personal errors include mathematical errors in
calculations and prejudice in estimating measurements.
COMMON DETERMINATE ERRORS
Errors of the method
• These are the most serious errors of analysis.
• Most of the above errors can be minimized or
corrected for but errors that are inherent in the
method cannot be changed, unless the conditions of
the determination are altered.
• Some sources of methodic errors include
coprecipitation of impurities, slight solubility of
precipitate, side reactions, incomplete reactions
• Sometimes correction can be relatively simple, for
example, by running a reagent blank
• It is standard practice to run such blanks and to
subtract the results from those for the sample
INDETERMINATE ERRORS
• Often called accidental or random errors which
represent the experimental uncertainty which occurs in
any measurement.
• These errors are revealed by small differences in
successive measurements made by the same analyst
under virtually identical conditions, and they cannot be
predicted or estimated.
• These accidental errors will follow a random
distribution, therefore mathematical laws of probability
can be applied to arrive at some conclusion regarding
the most probably result of a series of measurements
STATISTICS
Measures of central Tendency
• The mean, 𝑋 is the numerical average obtained by
dividing the sum of the individual measurements
by the number of measurements
𝑛
𝑖=1 𝑋𝑖
𝑋= 𝑖
𝑛
• where 𝑋𝑖 is the 𝑖 th measurement, and 𝑛 is the
number of independent measurements.
Question
What is the mean for the data in the Table below?
STATISTICS
Measures of central Tendency
• The median, 𝑋𝑚𝑒𝑑 , is the middle value when data
are ordered from the smallest to the largest value.
• When the data include an odd number of
measurements, the median is the middle value.
• For an even number of measurements, the median
is the average of the 𝑛 2 ,where 𝑛 is the number of
measurements.
• Question
• What is the median for the data in the Table
below?
STATISTICS
Measures of Spread
• The range, w, is the difference between the largest
and smallest values in the data set.
Range = 𝑤 = Xlargest – Xsmallest
• The range provides information about the total
variability in the data set, but does not provide any
information about the distribution of individual
measurements.
Question
What is the range for the data in the Table below?
STATISTICS
Measures of Spread
• The absolute standard deviation, s, describes the spread of individual
measurements about the mean and is given as
𝑛 2
𝑖=1 𝑋𝑖 − 𝑋
𝑠=
𝑛 −1
• Where 𝑋𝑖 is one of 𝑛 individual measurements, and 𝑋 is the mean.
• Frequently, the relative standard deviation, 𝑠𝑟 , is reported.
𝑠
𝑠𝑟 =
𝑋
• The percent relative standard deviation is obtained by multiplying 𝑠𝑟 by
100%.
Question
What are the standard deviation, the relative standard deviation, and the
percent relative standard deviation for the data in the Table below?
STATISTICS
Measures of Spread
• Variance - Another common measure of spread is
the square of the standard deviation, or the
variance.
• The square of the standard deviation (s2).
• The standard deviation, rather than the variance, is
usually reported because the units for standard
deviation are the same as that for the mean value.
Question
What is the variance for the data in the table below.
Masses of seven ingredients used in liquid soap production

Ingredient Mass (g)

1 3.080
2 3.094
3 3.107
4 3.056
5 3.112
6 3.174

7 3.198
STATISTICS
• confidence interval range of results around a mean
value that could be explained by random error.
𝑋𝑖 = 𝜇 ± 𝑧𝜎
• where the factor z accounts for the desired level of
confidence, 𝜎 is the standard deviation and 𝜇 is the
population mean.
STATISTICS
• Confidence limit – the limits of the range
(confidence interval).
• Confidence level – the likelihood that the true
value falls within the range, usually expressed as a
percent.
• The confidence limit is given by:
𝑡𝑠
Confidence limit = 𝑋 ± .
𝑁
Example:
• A soda ash sample is analysed in the analytical
chemistry laboratory by titration with standard
hydrochloric acid. The analysis is performed in
triplicate with the following results: 93.50, 93.58
and 93.43% Na2CO3. Within what range are you
95% confident that the true value lies?
Solution:
• The mean is 93.50%. The standard deviation s is
calculated to be 0.075% Na2CO3 (absolute). At the 95%
confidence level and two degrees of freedom. t = 4.303
and
𝑡𝑠
confidence limit = x ±
𝑁
4.303×0.075
= 93.50 ±
3
= 93.50 ± 0.19%
• So you are 95% confident that in the absence of a
determinate error, the true value falls within 93.31 –
93.69%.
 STATISTICS
Q – Test
Outlier - Data point whose value is much larger or smaller than the remaining
data.
• The Q-test compares the difference between the suspected outlier and its
nearest numerical neighbor to the range of the entire data set.
• Data are ranked from smallest to largest so that the suspected outlier is either
the first or the last data
• The test statistic, Qexp, is calculated using equation below if the suspected
outlier is the smallest value (X1)

𝑋2 − 𝑋1
𝑄𝑒𝑥𝑝 =
𝑋𝑛 − 𝑋1
or using the equation below if the suspected outlier is the largest value (Xn)
𝑋𝑛 − 𝑋𝑛 −1
𝑄𝑒𝑥𝑝 =
𝑋𝑛 − 𝑋1
where n is the number of members in the data set, including the suspected
outlier.
Example:
The following is a set of analyses on separate
aliquots of a pooled serum were reported: 103, 106,
107, and 114 meq/L. One value appears suspect.
Determine if it can be ascribed to accidental error, at
the 95% confidence level.
Solution:
The suspect result is 114 meq/L. It differs from its
nearest neighbour 107meq/L by 7 meq/L.
The range is 114 to 103 or 11meq/L.
Q is therefore 7/11 = 0.64.
The tabulated value for four observations is 0.829.
Since the calculated Q is less than the tabulated Q,
the suspected number may not be rejected.
STATISTICS- The Confidence Limit

• t-test statistical test for comparing two mean

values to see if their difference is too large to be
explained by indeterminate error.
𝑁
𝑡𝑒𝑥𝑝 = ±𝑡 = x − 𝜇
𝑠

Where t is statistical factor that depends on the

number of degrees of freedom and the confidence
level desired.
Example:
• You are developing a procedure for determining
traces of copper in biological materials using a wet
digestion followed by measurement by atomic
absorption spectrophotometry. In order to test the
validity of the method, you obtain a NIST orchard
leaves standard reference material and analyse this
material. Five replicas are sampled and analysed,
and the mean of the results is found to be 10.8ppm
with a standard deviation of ±0.7ppm. The listed
value is 11.7 ppm. Does your method give a
statistically correct value at the 95% confidence
level?
Solution:

𝑁
±𝑡 = x − 𝜇
𝑠

5
= 10.8 − 11.7
0.7
= 2.9

There are five measurements, so they are four degrees of freedom ( N –

1). From table we see that the tabulated value of t at the 95% confidence
level is 2.776. this is less than the calculated value, so there is a
determinate error in the new procedure. That is there is a 95% probability
that the difference between the reference value and the measured value
is due to chance.
STATISTICS
• F-test is used to determine if two variances are
statistically different
• F is defined in terms of variances of two methods,
where the variance is the square of the standard
deviation.
𝑠12
𝐹= 2
𝑠2
Where 𝑠12 > 𝑠22 . There are two different degrees of
freedom, 𝑣1 𝑎𝑛𝑑 𝑣2 , where degrees of freedom is
defined as 𝑁 − 1 for each case.
Example:
• You are developing a new coulometric procedure for
determining the glucose content of blood serum. You
have chosen the Folin - Wu procedure with which to
compare your results. From the following two sets of
replicate analyses on the same sample, determine
whether the variance of your method differs significantly
from that of the standard method.
Your Method, mg/dL Folin - Wu Method, mg/dL
127 130
125 128
123 131
130 129
131 127
126 125
129 ___
mean (x1 ) 127 mean (x2 ) 128
Solution:
2
x𝑖1 − x1 50
𝑠12 = = = 8.3
𝑁1 − 1 7 −1

x𝑖2 − x2 2 24
𝑠22 = = = 4.8
𝑁2 − 1 6 −1

8.3
𝐹= = 1.73
4.8
The variances are arranged so that the F value is > 1. The
tabulated F value for v1= 6 and v2 =5 is 4.95. Since the
calculated is less than this, we conclude that there is no
significant difference in the precision of the two methods, or
that the standard deviations are from random error alone and
don’t depend on the sample.
 LINEAR REGRESSION(Least
Squares) FOR GIVEN DATA
Linear Regression of Straight Line Calibration Curves
• When a calibration curve is a straight-line, we represent it
using the following mathematical equation:
• 𝑦 = 𝛽0 + 𝛽1 𝑥 (1)
• where y is the signal, Sstd, and x is the analyte’s concentration,
Cstd.
• The constants β0 and β1 are, respectively, the calibration
curve’s expected 𝑦-intercept and its expected slope.
• Because of uncertainty in our measurements,the best we can
do is to estimate values for β0 and β1, which we represent as
b0 and b1.
• The goal of a LINEAR REGRESSION analysis is to determine
the best estimates for b0 and b1.
 Unweighted Linear Regression
with Errors in y
• The most common approach to completing a linear
regression for equation (1) makes three
assumptions:
• (1) that any difference between our experimental
data and the calculated regression line is the result
of indeterminate errors affecting y,
• (2) that indeterminate errors affecting y are
normally distributed, and
• (3) that the indeterminate errors in y are
independent of the value of x.
Unweighted Linear Regression
with Errors in y
• Because we assume that the indeterminate errors
are the same for all standards,each standard
contributes equally in estimating the slope and the
y-intercept.
• For this reason the result is considered an
UNWEIGHTED LINEAR REGRESSION.
HOW A LINEAR REGRESSION
WORKS
 HOW A LINEAR REGRESSION
WORKS
• Illustration(previous slide) showing three data points
and two possible straight-lines that might explain the
data.
• The goal of a linear regression is to find the
mathematical model, in this case a straight-line, that
best explains the data.
• The equation for the solid line is
ŷ = 𝑏0 + 𝑏1 𝑥 (2)

where b0 and b1 are our estimates for the y-intercept and the
slope, and ŷ is our prediction for the experimental value of y
for any value of x.
• Assuming that all uncertainty is the result of
indeterminate errors affecting y, the difference between y
for each data ŷ point is the RESIDUAL ERROR, r, in our
mathematical model for a particular value of x.

(3)

The figure below shows the residual errors for the three
data points. The smaller
the total residual error, R, which we define as
 (4)

the better the fit between the straight-line and the data.
• In a linear regression analysis, we seek values of b0 and b1 that give the
smallest total residual error.
• Illustration (previous slide) showing the evaluation
of a linear regression in which we assume that all
uncertainty is the result of indeterminate errors
affecting y.
• The points in blue, 𝑦𝑖 , are the original data and the
points in red, ŷ𝑖 , are the predicted values from the
regression equation,
ŷ = 𝑏0 + 𝑏1 𝑥.
• The smaller the total residual error (equation 4),
the better the fit of the straight-line to the data.
FINDING THE SLOPE AND Y-
INTERCEPT
• Although we will not formally develop the mathematical
equations for a linear regression analysis, you can find the
derivations in many standard statistical texts. The resulting
equation for the slope, b1, is

(5)

• and the equation for the y-intercept, 𝑏0 , is

(6)

• Although equation 5 and equation 6 appear formidable, it is

only necessary to evaluate the following four summations
𝑥𝑖 𝑦𝑖 𝑥𝑖 𝑦𝑖 𝑥𝑖2
𝑖 𝑖 𝑖 𝑖
Example:
• Using the data from the table below, determine the
relationship between Sstd
• and Cstd using an unweighted linear regression.
Data for a Hypothetical Multiple-Point External
Standardization
Cstd Sstd kA Sstd/Cstd
0.000 0.00 –
0.100 12.36 123.6
0.200 24.83 124.2
0.300 35.91 119.7
0.400 48.79 122.0
0.500 60.42 122.8
mean value for kA = 122.5
Solution:
We begin by setting up a table to help us organize
the calculation.

Adding the values in each column gives

𝑥𝑖 = 1.500 𝑦𝑖 = 182.31 𝑥𝑖 𝑦𝑖 = 66.701 𝑥𝑖2 = 0.550
𝑖 𝑖 𝑖 𝑖
• Substituting these values into equation 5 and equation
6, we find that the slope and the y-intercept are,
6 × 66.701 − 1.500 × 182.31
𝑏1 = 2
= 120.706 ≈ 120.71
6 × 0.550 − 1.500

182.31 − 120.706 × 1.500

𝑏0 = = 0.209 ≈ 0.21
6
The relationship between the signal and the analyte,
therefore, is
Sstd = 120.71 × Cstd + 0.21
• For now we keep two decimal places to match the
number of decimal places in the signal.
• The resulting calibration curve is shown in the figure
below.
Calibration curve for the data in the table
above and for the example used above.
SAMPLING
AND SAMPLE
PREPARATION
HANDLING THE SAMPLE IN
THE LABORATORY
 Each sample should be completely identified,
tagged, or labeled so that no question as to its
origin or source can arise.
 Some of the information that may be on the
sample is as follows:
1. The number of the sample.
2. The notebook experiment-identification number.
3. The date and time of day the sample was received.
HANDLING THE SAMPLE IN THE LABORATORY

4. The origin of the sample and cross-reference

number.
5. The (approximate) weight or volume of the
sample.
6. The identifying code of the container.
7. What is to be done with the sample, what
determinations are to be made, or what analysis is
desired?
HANDLING THE SAMPLE IN THE LABORATORY

 A computerized laboratory data management

system is the solution for these problems.
 Information as to samples expected, tests to be
performed, people and instruments to be used,
calculations to be performed, and results required
are entered and stored directly in such a system.
 The raw experimental data from all tests can be
collected by the computer automatically or can be
entered manually.
 Status reports as to the tests completed, work in
progress, priority work lists, statistical trends, and
so on are always available automatically on
schedule and on demand.
 SAMPLING GASES
 The size of the gross sample required for gases can be
relatively small because any inhomogeneity occurs at
the molecular level.
Relatively small samples contain tremendous quantities
of molecules.
 The major problem is that the sample must be
representative of the entire lot.
 This requires the taking of samples with a “sample
thief” at various locations of the lot, and then
combining the various samples into one gross sample.
 SAMPLING GASES

 Gas samples are collected in tubes [250 to 1000 millilitres

(mL) capacity] that have stopcocks at both ends.
 The tubes are either evacuated or filled with water, or a
syringe bulb attachment may be used to displace the air
in the bottle by the sample.
 For sampling by the static method, the sampling bottle is
evacuated and then filled with the gas from the source
being sampled, perhaps a cylinder.
 These steps are repeated a number of times to obtain
the desired sampling accuracy.
 SAMPLING GASES
 For sampling by the dynamic method, the gas is allowed to
flow through the sampling container at a slow, steady rate.
 The container is flushed out and the gas reaches
equilibrium with the walls of the sampling lines and
container with respect to moisture.
 When equilibrium has been reached, the stopcocks on
the sampling container are closed—the exit end first
followed by the entrance end.
 The sampling of flowing gases must be made by a device
that will give the correct proportion of the gases in each
annular increment.
SAMPLING GASES
 Glass containers are excellent for inert gases such
as oxygen, nitrogen, methane, carbon monoxide,
and carbon dioxide.
 Stainless-steel containers and plastic bags are
also suitable for the collection of inert gases.
 Entry into the bags is by a fitting seated in and
connected to the bag to form an integral part of the
bag.
 Reactive gases, such as hydrogen sulfide, oxides
of nitrogen, and sulphur dioxide, are not
recommended for direct collection and storage.
 However, Tedlar bags are especially resistant to
wall losses for many reactive gases.
SAMPLING GASES
 In most cases of atmospheric sampling, large volumes
of air are passed through the sampling apparatus.
 Solids are removed by filters; liquids and gases are
either adsorbed or reacted with liquids or solids in the
sampling apparatus.
 A flow meter or other device determines the total
volume of air that is represented by the collected
sample.
 A manual pump that delivers a definite volume of air
with each stroke is used in some sampling devices.
SAMPLING LIQUIDS.
 For bottle sampling a suitable glass bottle of about
1-L capacity, with a 1.9-centimetre (cm) opening
fitted with a stopper, is suspended by clean cotton
twine and weighted with a 560-gram (g) lead or
steel weight.
 The stopper is fitted with another length of twine.
 At the appropriate level or position, the stopper is
removed with a sharp jerk and the bottle permitted
 to fill completely before raising. A cap is applied
to the sample bottle after the sample is
withdrawn.
SAMPLING LIQUIDS.
 In thief sampling a thief of proprietary design is used to
obtain samples from within about 1.25 cm of the tank
bottom.
 When a projecting stem strikes the bottom, the thief
opens and the sample enters at the bottom of the unit
and air is expelled from the top.
 The valves close automatically as the thief is
withdrawn.
 A core thief is lowered to the bottom with valves open
to allow flushing of the interior.
 The valves shut as the thief hits the tank bottom.
 SAMPLING LIQUIDS.
 When liquids are pumped through pipes, a number of
samples can be collected at various times and combined to
provide the gross sample.
 Care should be taken that the samples represent a constant
 fraction of the total amount pumped and that all portions of
the pumped liquid are sampled.
 Liquid solutions can be sampled relatively easily provided
that the material can be mixed thoroughly by means of
agitators or mixing paddles.
 Homogeneity should never be assumed.
 After adequate mixing, samples can be taken from the top
and bottom and combined into one sample that is
thoroughly mixed again; from this the final sample is taken
for analysis.
 SAMPLING LIQUIDS.
 For sampling liquids in drums, carboys, or bottles, an open-
ended tube of sufficient length to reach within 3mm of the
bottom of the container and of sufficient diameter to
contain from 0.5 to 1.0 L may be used.
 For separate samples at selected levels, insert the tube with
a thumb over the top end until the desired level is reached.
 The top hole is covered with a thumb upon withdrawing the
tube.
 Alternatively the sample may be pumped into a sample
container.
SAMPLING LIQUIDS.
 Specially designed sampling syringes are used to
sample micro quantities of air-sensitive materials.
 For suspended solids, zone sampling is very
important. A proprietary zone sampler is
advantageous.
 When liquids are pumped through pipes, a number
of samples can be collected at various times and
combined to provide the gross sample.
 Take care that the samples represent a constant
fraction of the total amount pumped and that all
portions of the pumped liquid are sampled.
 SAMPLING COMPACT SOLIDS.
 In sampling solids particle size introduces a variable.
 The size/weight ratio b can be used as a criterion of sample
size.
 This ratio is expressed as
weight of largest particle ×100
b=
weight of sample
 A value of 0.2 is suggested for b; however, for economy and
accuracy in sampling, the value of b should be determined
by experiment.
 SAMPLING COMPACT SOLIDS.
• The task of obtaining a representative sample from non-
homogeneous solids requires that one proceeds as follows.
• A gross sample is taken.
• The gross sample must be at least 454kg if the pieces are
greater than 2.54 cm, and must be subdivided to 1.90 cm before
reduction to 227 kg, to1.27 cm before reduction to 113 kg, and
so on, down to the 6.8-kg sample, which is sent to the
laboratory.
• Mechanical sampling machines are used extensively because
they are more accurate and faster than hand-sampling methods
described below.
• One type removes part of a moving steam of material all of the
time.
• A second type diverts all of stream of material at regular
intervals.
SAMPLING COMPACT SOLIDS.
 For natural deposits or semisoft solids in barrels,
cases, bags, or cake form, an auger sampler of
post-hole digger is turned into the material and
then pulled straight out.
 Core drilling is done with special equipment; the
driving head should be of hardened steel and the
barrel should be at least 46 cm long.
 Diamond drilling is the most effective way to take
trivial samples of large rock masses.
SAMPLING COMPACT SOLIDS.
 For bales, boxes, and similar containers, a split-tube
thief is used.
 The thief is a tube with a slot running the entire length
of the tube and sharpened to a cutting edge.
 The tube is inserted into the centre of the container
with sufficient rotation to cut a core of the material.
 For sampling from conveyors or chutes, a hand scoop is
used to take a cross-sectional sample of material while
in motion.
 A gravity-flow auger consists of a rotating slotted tube
in a flowing mass.
 The material is carried out of the tube by a worm
screw.
 SAMPLING METALS.
• Metals can be sampled by drilling the piece to be sampled
at regular intervals from all sides, being certain that each
drill hole extends beyond the halfway point.
• Additional samples can be obtained by sawing through the
metal and collecting the “sawdust.”
• Surface chips alone will not be representative of the entire
mass of a metallic material because of differences in the
melting points of the constituents.
• This operation should be carried out dry whenever
possible.
 SAMPLING METALS.
 If lubrication is necessary, wash the sample carefully with
benzene and ether to remove oil and grease.
 For molten metals the sample is withdrawn into a glass holder by
a sample gun.
 When the sample cools, the glass is broken to obtain the
sample.
 In another design the sampler is constructed of two concentric
slotted brass tubes that are inserted into a molten or powdered
mass.
 The outer tube is rotated to secure a representative solid core.
MIXING AND REDUCTION OF
SAMPLE VOLUME
• The sample is first crushed to a reasonable size and a
portion is taken by quartering or similar procedures.
• The selected portion is then crushed to a somewhat
smaller size and again divided.
• Theoperations are repeated until a sample is obtained
that is large enough for the analyses to be made but
not so large as to cause needless work in its final
preparation.
• This final portion must be crushed to a size that will
minimize errors in sampling at the balance yet is fine
enough for the dissolution method that is
contemplated.
 MIXING AND REDUCTION OF SAMPLE
VOLUME
 Every individual sample presents different problems in
regard to splitting the sample and grinding or crushing the
sample.
 If the sample is homogeneous and hard, the splitting
procedure will present no problems but grinding will be
difficult.
 If the sample is heterogeneous and soft, grinding will be
easy but care will be required in splitting.
 When the sample is heterogeneous both in composition
and hardness, the interactions between the problems of
splitting and grinding can be formidable.
 Splitting is normally performed before grinding in order to
minimize the amount of material that has to be ground to
the final size that is suitable for subsequent analysis.
CONING AND QUARTERING
 A good general method for mixing involves pouring
the sample through a splitter repeatedly, combining
the two halves each time by pouring them into a
cone.
 When sampling very large lots, a representative
sample can be obtained by coning and quartering.
 The first sample is formed into a cone, and the
next sample is poured onto the apex of the cone.
 The result is then mixed and flattened, and a new
cone is formed.
 CONING AND QUARTERING
 As each successive sample is added to the re-formed cone,
the total is mixed thoroughly and a new cone is formed prior
to the addition of another sample.
 After all the samples have been mixed by coning, the mass is
flattened and a circular layer of material is formed.
 This circular layer is then quartered and the alternate
quarters are discarded.
 This process can be repeated as often as desired until a
sample size suitable for analysis is obtained.
Coning samples.
CONING AND QUARTERING
• After all the samples have been mixed by coning,
the mass is flattened and a circular layer of material
is formed.
• This circular layer is then quartered and the
alternate quarters are discarded.
• This can be repeated as often as desired until a
sample size suitable for analysis is obtained.
 CONING AND QUARTERING
• The method is easy to apply when the sample is received as
a mixture of small, equal-sized particles.
• Samples with a wide range of particle sizes present more
difficulties, especially if the large, intermediate, and small
particles have appreciably different compositions.
• It may be necessary to crush the whole sample before
splitting to ensure accurate splitting.
• When a coarse sized material is mixed with a fine powder of
greatly different chemical composition, the situation
demands fine grinding of a much greater quantity than is
normal, even the whole bulk sample in many cases.
• Errors introduced by poor splitting are statistical in nature
and can be very difficult to identify except by using duplicate
samples.
 RIFFLES
• Riffles are also used to mix and divide portions of the
sample.
• A riffle is a series of chutes directed alternately to opposite
sides.
• The starting material is divided into two approximately
equal portions.
• One part may be passed repeatedly through until the
sample size is obtained.
RIFFLES

Quartering samples.
CRUSHING AND GRINDING
Introduction
 In dealing with solid samples, a certain amount of
crushing or grinding is sometimes required to
reduce the particle size.
 Unfortunately, these operations tend to alter the
composition of the sample and to introduce
contaminants.
 For this reason the particle size should be reduced no
more than is required for homogeneity and ready
attack by reagents.
 If the sample can be pulverized by impact at room
temperature, the choices are the following:
 CRUSHING AND GRINDING
1.Shatterbox for grinding 10 to 100 mL of sample.
2. Mixers or mills for moderate amounts to micro samples.
3. Wig-L-Bug for quantities of 1 mL or less.
• For brittle materials that require shearing as well as impact,
use a hammer–cutter mill for grinding wool, paper, dried
plants, wood, and soft rocks.
• For flexible or heat-sensitive samples, such as polymers or
tissues, chill in liquid nitrogen and grind in a freezer mill or
use the shatterbox that is placed in a cryogenic container.
• For hand grinding, use boron carbide mortars.
 PULVERIZING AND BLENDING
Reducing the raw sample to a fine
powder is the first series of steps in
sample handling.
 Sample reduction equipment is shown in
Table 1.1, and the properties of which are
given in Table 1.2.
 CONTAINMENT MATERIALS.
 The containers for pulverizing and blending must be harder than
the material being processed and should not introduce a
contaminant into the sample that would interfere with
subsequent analyses.
 The following materials are available.
 Agate is harder than steel and chemically inert to almost
anything except hydrofluoric acid.
 Although moderately hard, it is rather brittle.
 Use is not advisable with hard materials, particularly aluminum-
containing samples, or where the silica content is low and
critical; otherwise agate mortars are best for silicates.
 Agate mortars are useful when organic and metallic
contaminations are equally undesirable.
 Silicon is the major contaminant, accompanied by traces of
aluminum, calcium,iron, magnesium, potassium, and sodium.
 CONTAINMENT MATERIALS
• Alumina ceramic is ideal for extremely hard samples,
especially when impurities from steel and tungsten carbide
are objectionable.
• Aluminum is the major contaminant, accompanied by
traces of calcium, magnesium, and silicon.
• However, because alumina ceramic is brittle, care must be
taken not to feed “uncrushable” materials such as scrap
metal, hardwoods, and so on into crushers or mills.
 CONTAINMENT MATERIALS
 Boron carbide is very low wearing but brittle. It is probably
most satisfactory for general use in mortars, although
costly.
 Major contaminants are boron and carbide along with
minor amounts of aluminum, iron, silicon, and possibly
calcium.
 The normal processes of decomposition used in
subsequent stages of the analysis usually convert the boron
carbide contaminant into borate plus carbon dioxide, after
which it no longer interferes with the analysis.
 Plastic containers (and grinding balls) are usually
methacrylate or polystyrene.
 Only traces of organic impurities are added to the
sample.
 Steel (hardened plain-carbon) is used for general-
purpose grinding.
 Iron is the major contaminant, accompanied by traces
of carbon, chromium, manganese, and silicon.
 Stainless steel is less subject to chemical attack, but
contributes nickel and possibly sulfur as minor
contaminants.
 CONTAINMENT MATERIALS
 Tungsten carbide containers are the most effective and versatile
of all.
 Containers are long wearing but subject to breakage.
 Grinding is fast and contamination is minimal.
 Major contaminants are tungsten, carbon, and cobalt (a binder);
minor contaminants are tantalum, titanium, and niobium.
 The level of contamination introduced into a hard rock or
ceramic sample may well be an appreciable
fraction of 1% of the total weight.
 Zirconia is hard and tough, and wears slowly.
 Contaminants are zirconium with traces of magnesium and
hafnium.
 Halide-releasing compounds must be ground in agate, alumina,
plastic, or tungsten carbide containers.
BALL OR JAR MILL.
 Ball or jar mills are jars or containers that are fitted
with a cover and gasket that are securely fastened to
the jar.
 The jar is half filled with special balls, and then enough
of the sample is added to cover the balls and the voids
between them.
 The cover is fastened securely and the jar is revolved
on a rotating assembly.
 The length of time for which the material is ground
depends upon the fineness desired and the hardness of
the material.
 After pulverization the jar is emptied onto a coarse-
mesh screen to separate the balls from the ground
material.
 For small samples, vials from 2.54- to 6.37-cm long
and up to 1.9 cm in diameter use methacrylate
balls 0.12 to 0.30 to 0.97 cm in diameter,
respectively.
 A 2.54-cm motion along the axis of the vial is
complemented by two motions at right angles to
the vial axis: a 0.48-cm horizontal movement and a
0.635-cm vertical oscillation.
 DRYING SAMPLES
 Samples may be dried by heating them to 110°C or higher if the
melting point of the material is higher and the material will not
decompose at that temperature.
 This procedure will remove the moisture bound to the surface of
the particles.
The procedure for drying samples is as follows:
1. Fill the weighing bottle no more than half full with the sample
to be dried.
2. Place a label on the beaker or loosely inside the beaker.
 Do not place a label on the weighing bottle as it will gradually
char.
3. Place the weighing bottle in the beaker.
 Remove the cover from the weighing bottle and place it inside
the beaker.
DRYING SAMPLES
4. Cover the beaker with a watch glass supported on
glass hooks.
5. Place the beaker with weighing bottle in a drying
oven at the desired temperature for 2 hours (h).
6. Remove the beaker from the oven.
• Cool it somewhat before placing the weighing
bottle, now covered with its cap, in a desiccator.
 THE DESICCATOR.
 A desiccator is a container (glass or aluminum) filled with a substance
that absorbs water (a desiccant).
 The ground-glass (or metal) rim is lightly greased with petroleum jelly
or silicone grease.
 The desiccator provides a dry atmosphere for objects and substances.
 The desiccator’s charge of desiccant must be frequently renewed to
keep it effective.
 Surface caking signals the need to renew.
 Some desiccants contain a dye that changes color upon exhaustion.
 Vacuum desiccators are equipped with side arms so that they may be
connected to a vacuum.
 This type of desiccator should be used to dry crystals that are wet
with organic solvents.
 Vacuum desiccators should not be used for substances that sublime
readily.
 METHODS FOR DISSOLVING THE
SAMPLE
Introduction
 Relatively few natural materials or organic materials are water
soluble; they generally require treatment with acids or mixtures
of acids, some combustion treatment, or even a fusion with
some basic or acidic flux.
 The procedure adopted for the solution of a material will
depend on the speed and convenience of the method and
reagents employed and the desirability of avoiding the
introduction of substances that interfere with the subsequent
determinations or are tedious to remove.
 Consideration must also be given to the possible loss during the
solution process of the constituents to be determined.
 For trace analysis it is desirable to minimize the amounts of
reagents that restrict the choices available for sample
decomposition.
 METHODS FOR DISSOLVING THE
SAMPLE
 To determine the elemental composition of an organic
substance requires drastic treatment of the material in
order to convert the elements of interest into a form
susceptible to the common analytical techniques.
 These treatments are usually oxidative in nature and involve
conversion of the carbon and hydrogen of the organic
material to carbon dioxide and water.
 In some instances, however heating the sample with a
potent reducing agent is sufficient to rupture the covalent
bonds in the compound and free the element to be
determined from the carbonaceous residue.
METHODS FOR DISSOLVING THE
SAMPLE
 Oxidation procedures are divided into two
categories.
 Wet-ashing (or oxidation) uses liquid oxidizing
agents.
 Dry-ashing involves ignition of the organic
compound in air or a stream of oxygen.
 Oxidations can also be carried out in fused-salt
media; sodium peroxide is the most common flux
for this purpose.
DECOMPOSITION OF INORGANIC
SAMPLES
 All metals below hydrogen displace
 hydrogen and dissolve in non-oxidizing acids with
the evolution of hydrogen.
 The action of hydrochloric acid on lead, cobalt,
nickel, cadmium, and chromium is slow,and lead is
insoluble in sulfuric acid owing to the formation of
a surface film of lead sulfate.
 Oxidizing acids must be used to dissolve the metals
above hydrogen.
DECOMPOSITION OF INORGANIC
SAMPLES
 Oxidizing acids must be used to dissolve the metals
above hydrogen.
 The most common of the oxidizing acids are nitric acid,
hot concentrated sulfuric acid, hot concentrated
perchloric acid, or some mixture that yields free
chlorine or bromine.
 Addition of bromine or hydrogen peroxide to mineral
acids is often useful.
 Considerable difficulties are encountered in the
dissolution of inorganic matrices such as oxides,
silicates, nitrides, carbides, and borides, problems often
encountered in the analysis of geological samples and
ceramics.
 USE OF LIQUID REAGENTS
Water
 . It should come as no surprise that ordinary water can be
an excellent solvent for many samples.
 Due to its extremely polar nature, water will dissolve most
substances of likewise polar or ionic nature.
 Obviously, then, when samples are composed solely of
ionic salts or polar substances, water would be an excellent
choice.
 An example might be the analysis of a commercial iodized
table salt for sodium iodide content.
 USE OF LIQUID REAGENTS
 Use of Hydrochloric Acid.
 Concentrated hydrochloric acid (about 12M) is an excellent
solvent for many metal oxides as well as those metals that lie
below hydrogen in the electro motive series.
 It is often a better solvent for the oxides than the oxidizing acids.
Hydrochloric acid dissolves the phosphates of most of the
common metals although the phosphates of niobium, tantalum,
thorium, and zirconium dissolve with difficulty.
 Hydrochloric acid decomposes silicates containing a high
proportion of strong or moderately strong bases but acidic
silicates are not readily attacked.
 The concentrated acid dissolves the sulphides of antimony,
bismuth, cadmium, indium, iron, lead, manganese, tin, and zinc;
cobalt and nickel sulphides are partially dissolved.
 Addition of 30% hydrogen peroxide to hydrochloric acid often
aids the digestion of metals due to the release of nascent
chlorine.
DECOMPOSITION OF INORGANIC
SAMPLES
• After a period of heating in an open container, a
constant-boiling 6M solution remains (boiling point
about 112°C).
• The low boiling point of hydrochloric acid limits its
efficiency to dissolve oxides.
 DECOMPOSITION OF INORGANIC
SAMPLES
Use of Hydrofluoric Acid.
 The primary use for hydrofluoric acid is the decomposition
of silicate rocks and minerals in which silica is not to be
determined; the silicon escapes as silicon tetrafluoride.
 After decomposition is complete, the excess hydrofluoric
acid is driven off by evaporation with sulfuric acid to fumes
or with perchloric acid to virtual dryness.
 Sometimes residual traces of fluoride can be complexed
with boric acid.
 DECOMPOSITION OF INORGANIC
SAMPLES
Use of Hydrofluoric Acid.
 Hydrofluoric acid dissolves niobium, tantalum, and zirconium,
forming stable complexes, although the action is sometimes
rather slow.
 Hydrofluoric acid is an excellent solvent for the oxides of these
metals although the temperature to which the oxide has been
heated has a notable effect.
 Indium and gallium dissolve very slowly.
 Caution :Hydrofluoric acid can cause serious damage and painful
injury when brought in contact with the skin.
 Momentarily it acts like a “painkiller” while it penetrates the
skin or works under fingernails.
DECOMPOSITION OF INORGANIC
SAMPLES
Use of Nitric Acid.
 Concentrated nitric acid is an oxidizing solvent that
finds wide use in attacking metals.
 It will dissolve most common metallic elements
except aluminum, chromium, gallium, indium, and
thorium, which dissolve very slowly because a
protective oxide film forms.
 Nitric acid does not attack gold, hafnium,
tantalum, zirconium, and the metals of the
platinum group (other than palladium).
DECOMPOSITION OF INORGANIC
SAMPLES
 Many of the common alloys can be decomposed by
nitric acid.
 However, tin, antimony, and tungsten form insoluble
oxides when treated with concentrated nitric acid.
 This treatment is sometimes employed to separate
these elements from other sample components.
 Nitric acid attacks the carbides and nitrides of
vanadium and uranium.
 Nitric acid is an excellent solvent for sulfides although
the sulphides of tin and antimony form insoluble acids.
 Mercury(II) sulphide is soluble in a mixture of nitric acid
and hydrochloric acid.
DECOMPOSITION OF INORGANIC
SAMPLES
 Although nitric acid is a good oxidizing agent, it
usually boils away before the sample is completely
oxidized.
 A mixture of nitric and hydrofluoric acids dissolves
hafnium, niobium, tantalum, and zirconium readily.
 This mixture is also effective with antimony, tin,
and tungsten; the carbides and nitrides of niobium,
tantalum, titanium, and zirconium; and the borides
of zirconium.
 DECOMPOSITION OF INORGANIC
SAMPLES
Use of Sulphuric Acid.
Hot concentrated sulfuric acid is often employed as a solvent.
 Part of its effectiveness arises from its high boiling point (about
340°C), at which temperature decomposition and solution of
substances often proceed quite rapidly.
 Most organic compounds are dehydrated and oxidized under these
conditions.
 Most metals and many alloys are attached by the hot acid.
 Digestions are completed often in 10 min using sulphuric acid and
50% hydrogen peroxide (4 mL + 10 mL) with the Digesdahl digestion
apparatus .
 Fumes are removed by connecting the fractionating column to either
a water aspirator or a fume scrubber.
 DECOMPOSITION OF INORGANIC
SAMPLES
Use of Perchloric Acid.
 Hot concentrated perchloric acid (72%) is a potent oxidizing agent and
solvent.
 It attacks a number of ferrous alloys and stainless steels that are
intractable to the other mineral acids. In fact, it is the best solvent for
stainless steel, oxidizing the chromium and vanadium to the
hexavalent and pentavalent acids, respectively.
 In ordinary iron and steel, the phosphorus is completely oxidized with
no danger of loss.
 Sulphur and sulphides are oxidized to sulphate.
 Silica is rendered insoluble, and antimony and tin are converted to
insoluble oxides.
 Perchloric acid fails to dissolve niobium, tantalum, zirconium, and the
platinum group metals.
 Powdered tungsten and chromite ore are soluble in a boiling mixture
of perchloric and phosphoric acids.
DECOMPOSITION OF INORGANIC
SAMPLES
Use of Perchloric Acid.
• Cold perchloric acid and hot dilute solutions are
quite safe.
• However, all treatment of sample with perchloric
acid should be done in specially designed hoods
and behind explosion shields.
DECOMPOSITION OF INORGANIC
SAMPLES
• Aqua regia
• An acid mixture that is prepared by mixing one part
concentrated HNO3with three parts concentrated
HCl is called aqua regia.
• This mixture is among the most powerful
dissolving agents known.
• It will dissolve the very noble metals (gold and
platinum) as well as the most stable of alloys.
Fusion
• For extremely difficult samples, a method called
fusion may be employed.
• Fusion is the 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.
• The dissolving power of the flux is mostly due to
the extremely high temperatures (usually 300 to
1000℃) required to render most inorganic salts
molten.
 Fusion
 Additional problems arise within fusion methods, however.
 One is the fact that the flux must be present in a fairly large
quantity in order to be successful.
 The measurement of the analyte must not be affected by
this large quantity.
 Also, while a flux may be an excellent solvent for difficult
samples, it will also dissolve the container to some extent,
creating contamination problems.
 Platinum crucibles are commonly used, but nickel, gold, and
porcelain have been successfully used for some
applications.
 Fusion
• Probably the most common fluxes are sodium carbonate
(Na2CO3 ), ,lithium tetraborate (Li2B4O7), and lithium
metaborate (LiBO2).
• Fluxes may be used by themselves or in combination with
other compounds, such as oxidizing agents (nitrates,
chlorates, and peroxides).
• Applications include silicates and silica based samples and
metal oxides.
• For dissolving particularly difficult metal oxides, the acidic
flux potassium pyrosulphate (K2S2O7) maybe used.
 Decomposition of Organic
Compounds
• Analysis of the elemental composition of an organic substance
generally requires drastic treatment of the material in order to convert
the elements of interest into a form susceptible to the common
analytical techniques.
• These treatments are usually oxidative in nature, involving conversion
of the carbon and hydrogen of the organic material to carbon dioxide
and water.
• In some instances, however, heating the sample with a potent
reducing agent is sufficient to rupture the covalent bonds in the
compound and free the element to be determined from the
carbonaceous residue.
• Oxidizing procedures are sometimes divided into two categories.
• Wet-ashing (or oxidation) makes use of liquid oxidizing agents.
• Dry-ashing usually implies ignition of the organic compound in air or a
stream of oxygen. In addition, oxidations can be carried out in certain
fused-salt media, sodium
peroxide being the most common flux for this purpose.