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CHM421 – Analytical Chemistry

Topic 3: Sampling & Evaluation
of Experimental Data
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3.1 : Sampling

Purpose of SAMPLING ???

The purpose of SAMPLING is to obtain a REPRESENTATIVE SAMPLES of the

whole sample that can be taken to the laboratory for chemical analysis and the results
obtain will be ACCURATE.

In a chemical analysis:
A chemical analysis is usually performed on only small portion of the material or substance collected to be
characterized.
If the amount of material is very small and it is not needed for further use, then the entire samples may be
used for analysis.
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3.1 : Sampling

SAMPLING – Water Sampling

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3.1 : Sampling

SAMPLING – Solid Sampling

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3.1 : Sampling

SAMPLING – Air Sampling

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3.1 : Sampling

Sampling

Air Sampling
Solid Sampling

Liquid Sampling
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3.1.1 : Methods for Sampling Solid, Liquid & Gas
Solid

o Inhomogeneity of the solid sample, variation in sample size and variation

within the particle size make sampling of solids more difficult then other material.

o The easiest but usually the most unreliable way to sample a solid material is by the
grab sample, which is one sample taken at random and assume to be
representative.
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3.1.1 : Methods for Sampling Solid, Liquid & Gas
Solid

o Solid samples usually need further treatment.

Example if ores are being sampled, first crush the ore to a smaller size and
then sieve and use the QUARTERING TECHNIQUE to get the right sample
size to the laboratory.

o Solid samples may need drying.

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3.1.1 : Methods for Sampling Solid, Liquid & Gas

Purpose of drying solid samples:

oTo ensure that the exact weight is obtained during the QUANTITATIVE chemical analysis.
oHow it is done :

 Solid samples dried in oven at 105 – 110 oC for 1- 2 hours.

 Plant and tissue samples dried by heating

Problems associated with drying of samples:

oSamples might decompose at high temperature
oSome samples are sensitive to heat, therefore drying can be carried out in a desiccators
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3.1.1 : Methods for Sampling Solid, Liquid & Gas

Quartering Technique
VIDEO
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3.1.1 : Methods for Sampling Solid, Liquid & Gas
Liquid

o Liquid samples tend to be homogeneous and are more easier to sample.

o Liquids mix by diffusion only very slowly and must be shaken to obtain a homogeneous mixture.

o If water sample is taken from the river, then the water samples is collected at the SURFACE,
MIDDLE and at the BOTTOM of the river bed.

o If the liquid is in a large container, then the liquid should be stirred first before the samples are taken
at the top, middle and at the bottom of the container.
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3.1.1 : Methods for Sampling Solid, Liquid & Gas
Air

1. Grab sampling:
oAn actual sample of air is taken in a flask, bottle, bag
or other suitable container. Done over a period of few
seconds or up to 1-2 minutes.

2. Continuous or integrated sampling:

oGases or vapours are removed from the air over a
measured time-period and concentrated by passage
through a solid or liquid sorbent.
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3.1.2 : Reduction to laboratory size sample
Samples storage
Purpose:
o There is a time gap between when the sample is taken and the actual analysis is being carried out.

o For liquids samples, make sure that it is kept in bottles with stoppers.

o Acidic liquid samples can be stored in glass container whereas basic liquid samples in plastic
container.

o Solid samples is easier to keep and have less chance to be adulterated by foreign matters.

o Sometimes it can also get absorbed or adsorbed to the wall of the container.
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3.1.2 : Reduction to laboratory size sample
Problems that encounters during storage of sample

oThe sample can be adulterated / contaminated by foreign matter.

oThere is a lost of analyte during storage.
oDecomposition of sample.
oSide reactions can occur. Example in the air pollution studies the content of SO 2 in air is not stable
due to the following reaction:
2SO2 + O2  2SO3
- to avoid the above reaction the sample is cooled to 4oC
oThe sample should not react with the wall of the container or get adulterated.
oDuring storage of liquid samples, sometimes there is a lost of analyte if it is volatile. So the
container should be closed tightly.
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3.1.2 : Reduction to laboratory size sample

Replicates sample

oMost chemical analyses are performed on replicate samples whose weights or volumes have been determined by
careful measurements with an analytical balance or with a precise volumetric device.

oObtaining replicate data on samples improves the quality of the results and provides a measure of their reliability.
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3.1.3 : Techniques to analyse samples

Using solution
oMost analyses are performed on solution of the sample. Ideally, the solvent should
dissolve the entire sample rapidly.

Using solid
oAshing - defined as the heating of a substance to leave only noncombustible ash,
which is analyzed for it's elemental composition

WET ASHING, DRY ASHING, MICROWAVE,

FUSIONS.
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3.1.3 : Techniques to analyse samples
Advantages of ashing Disadvantages of ashing

oThe ability to decompose large sample sizes. oLosses due to retention to the ashing container.
oLittle or no reagents is required. oLosses due to volatilization.
oThe technique is relatively safe. oContamination from the ashing container.
oThe ability to prepare samples containing oContamination from the muffle furnace.
volatile combustion elements such as sulfur, oPhysical loss of 'low density' ashes when the
fluorine and chlorine (the Schöniger oxygen muffle door is opened (air currents).
flask combustion technique is very popular in oDifficulty in dissolving certain metal oxides.
this case).
oFormation of toxic gases in poorly ventilated
oThe technique lends itself to mass areas. (Note that all charring should take place in a
production. hood and the muffle furnace must have a hood
canopy for proper ventilation).
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3.1.3 : Techniques to analyse samples
a procedure for oxidizing organic substances
by using acids and oxidizing agents or their
combinations. Minerals are solubilized without volatilization.

Wet Ashing

oTo treat solid sample by acid digestion, producing clear solution with no loss
of the element to be determine.
oStrong mineral acids are good solvents for many inorganics.
oHydrochloric acid, nitric acid or aqua regia (3:1, HCl:HNO3) dissolve many
inorganic substances.
oHF acid decompose silicates.
oPerchloric acid is used to break up organic complexes.
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Wet Ashing Method

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3.1.3 : Techniques to analyse samples
Dry Ashing (gravimetric)
oPerformed by weighed sample in crucible, heated in muffle furnace then the residue is dissolve in
suitable acid.

oTypical ashing temperatures are 450 to 550 C. Magnesium nitrate is commonly used as an ashing
aid.

oCharring the sample prior to muffling is preferred. Charring is accomplished using an open flame.

oCare must be taken to ensure that non of the volatile elements (Hg, Arsenic, Pb) from escaping
during ashing.

oDry ashing often used to remove organic substances from interfering with the analyte.
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Dry Ashing Method

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3.1.3 : Techniques to analyse samples
Microwave

oIn some cases the dissolution of sample can be done by using microwave oven to accelerate the dissolution process (at
microwaves T = 100 to 250 C or power = 700 to 900 W).
oThe sample is sealed in specially designed microwave digestion vessel with a mixture of appropriate acids.
oMicrowave ovens can be used for rapid and efficient drying and acid decomposition of samples.
oAdvantages of microwave digestions include reduction in times from hours to minutes and low blank levels due to reduced
amounts of reagents required.
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3.1.3 : Techniques to analyse samples
Fusion

oA weighed sample is mixed with a flux (sodium peroxide) in a metal (zirconium) or graphite
crucible. The mixture is heated over a flame, or in furnace and the resulting fused material is
leached with either water or appropriate acid (dilute mineral acid) or alkali.
(VIDEO)
oThese techniques are required for sample types that are inorganic in nature and unreactive toward
acid decomposition
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3.1.3 : Techniques to analyse samples

Fusions are considered to be more of a 'last resort' by trace analysts because:

 They are expensive and often not available (high purity fluxes).
 They yield high solids solutions that can salt out in the nebulizer.
 Large dilutions of the sample are a necessity.
 They often require expensive equipment.
 Spectral interferences from the flux and/or crucible construction material must be considered.
 Contamination of the sample with the crucible construction element and impurities must be
considered.
 They are labor intensive.
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3.1.4 : Elimination of interference

Remove substances from the sample that may interfere with the measurement step.

oDistillation
oMasking agent
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3.2 : Evaluation of experimental data
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3.2.1 : Types & sources of error

Types of error

Systematic Error Random Error

What is?
Sources?
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3.2.1 : Types & sources of error

Determinate or Systematic Error

oAll measuring devices are sources of determinate errors.

oDeterminate error have a definite source that usually can be identified.

oThey cause all the results from replicate measurements to be either high or low.

oDue to the results are either high or low, determinate errors are also called
systematic errors.
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3.2.1 : Types & sources of error

3 sources of determinate or systematic errors:

oOperational and personal errors

oMethod errors

oInstrument and reagents error

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3.2.1 : Types & sources of error

Personal errors

Many measurements require personal judgments. Examples include:

oestimating the position of a pointer between two scale division, the colour of a
solution at endpoint in a titration
oIncorrect reading of meniscus
oBias is another source of personal error that varies considerable from person to
person
oInability to correctly followed procedures, such as weighing sample without waiting
for a complete drying in a gravimetric analysis
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3.2.1 : Types & sources of error

Method errors

Most serious error since difficult to detect. For example:

othe slowness of some reactions
othe incompleteness of reactions
othe instability of some species
othe non-specificity of most reagents
othe possible occurrence of side reactions that interfere with the measurement
process
A common method error in volumetric methods results from the small excess of reagent required to cause an
indicator to undergo the colour change that signals completion of reaction.
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3.2.1 : Types & sources of error

Instrument and reagents error

All measuring devices are sources of determinate errors. For example:

oImproperly calibrated - pipettes, burettes and volumetric flasks may have volumes
slightly different from those indicated by their graduations
oglassware at a temperature that differs significantly from the calibration
temperature
ofrom contaminants on the inner surface of the containers
oUse of reagents containing known amount of impurities
ofaulty balances
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3.2.1 : Types & sources of error

How to avoid determinate or systematic errors

oFrequent Calibration of apparatus (6 monthly)

oRuns a blank determination – separate experiment excluding the sample under

study.

oRuns a control determination – separate experiment using known standards under

similar conditions to the comparative experiment

oUse of independent methods of analysis – can check accuracy of results

oRuns parallel determinations – against single determinations

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3.2.1 : Types & sources of error

How to avoid determinate or systematic errors

oFrequent Calibration of apparatus (6 monthly)

oRuns a blank determination – separate experiment excluding the sample under

study.

oRuns a control determination – separate experiment using known standards under

similar conditions to the comparative experiment

oUse of independent methods of analysis – can check accuracy of results

oRuns parallel determinations – against single determinations

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3.2.1 : Types & sources of error
•Random error causes one measurement to differ
slightly from the next. It comes from
Random / Indeterminate errors unpredictable changes during an experiment.

oRandom or indeterminate errors occur when a system of measurement is extended to its maximum
sensitivity (successive measurements)

oThey are cause by the many uncontrollable variables that are an inevitable part of every physical and
chemical measurement

oThe detection of this type of errors is difficult because they are VERY SMALL and non of them
can be positively identified or measured

oThe indeterminate errors are responsible for DEVIATIONS that occur in a series of experimental
data.
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3.2.2 : Mean, median, precision & accuracy

Statistical procedures to handle

analytical data

 Mean
 median
 range
 precise and deviations
 accurate and error
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3.2.2 : Mean, median, precision & accuracy

Mean (average)

x
Mean is the average reading of all data or measurements that are obtained from
an experiments.

Mean can be calculated by dividing the sum of replicate measurements by the

number of measurements in the set.
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3.2.2 : Mean, median, precision & accuracy

Mean for sample

 xi
x= i 1
n

where n is the number of samples.

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3.2.2 : Mean, median, precision & accuracy

Median
o It is a value that is in the middle of a set of data.
o Median of a set of replicate data is the middle result when the data are arranged
by increasing in size.

Range
o The highest value – the lowest value.
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3.2.2 : Mean, median, precision & accuracy

ACCURACY
o Accuracy is how close a measured value is to the actual (true) value or expert
value which we believe to be correct.

o Expressed in terms of ERROR/ABSOLUTE ERROR.

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3.2.2 : Mean, median, precision & accuracy
Precision
o Precision is how close the measured values are to each other measurements that
have been made in exactly the same way.
o Precision describes the reproducibility of results, that is the agreement between
two or more.
o Expressed in terms of DEVIATION
o If the DEVIATION between the measurements is small, then your works are
precise.

Deviation = (Value obtained - Mean Value) = ( xi - )x

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3.2.2 : Mean, median, precision & accuracy
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3.2.2 : Mean, median, precision & accuracy

Error = (Value obtained - True Value)

o If the error is small, then our measurements are accurate and it shows the
accuracy of the results obtained.

o Usually the errors are reported as % error or relative error.

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3.2.2 : Mean, median, precision & accuracy
Absolute error, E Relative error, Er
E =  xi - x t  xi - x t X 100%
Er =
where xi value obtained experimentally, xt *or part per
thousand
xt is the true value.

The sign of absolute error indicate whether the value in question

is either high or low as compared to true value.

Example 1: The results of an analysis are 36.97 g, compared with the accepted value of 37.06 g.
What is the relative error in part per thousand? [Answer:  2.4 part per thousand]
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3.2.3 : Standard deviation
Sample & Population

• SAMPLE • POPULATION
• A SMALL set of data (<20) • LARGE SET of data (>20)

n
N
 xi  xi
x = i1 µ= i1
n N

where n is the number of where N is very large for real

Samples that is usually small. population number.
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3.2.2 : Standard deviation
THE SAMPLE STANDARD
DEVIATION,(s)

The Standard Deviation, (s) is a more

n 2
s=  (x  x )
significant quantity in that it measures the
i precision or scatter of sample data set
i 1
n 1
The n – 1 term represents the degree of
freedom. In the calculation of standard
deviation, the degree of freedom is reduced
by ONE.

Example 2: Calculate the mean and the standard deviation of the following set of analytical results:
15.67 g, 15.69 g, 16.03 g. [Answer: x = 15.80, s = 0.20 g]
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3.2.4 : Significant figure & uncertainty

o Zeros between nonzero digits are significant.

508 cm has 3 significant figures.

o Leading zeroes merely locate the decimal point and are never
significant.
0.0497 cm equals 4.97 x 10-2 cm and has 3 significant figures.

o Trailing zeros are significant as follows:

50.0 mL has 3 significant figures,
50. mL has 2 significant figures,
and 50 mL has 1 significant figure.
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3.2.4 : Significant figure & uncertainty

Datum Number of Datum Number of

(grams) Significant (milliliters) Significant
Figures Figures
10,034 5 150. 3
1.908 4 0.705 3
0.32 2 0.054 2
0.00046 2 5.86 x 10-7 3
150 2 3040 3
0.0000160 3 0.0000730 3
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3.2.4 : Significant figure & uncertainty

o When adding or subtracting do NOT extend the result beyond the first column with a doubtful
figure. For example:
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3.2.4 : Significant figure & uncertainty

o What is 16.874 + 2.6?

o What is 16.874 - 2.6?

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3.2.4 : Significant figure & uncertainty
o When multiplying or dividing the answer will have the same number of
significant digits as the least accurate number used to get the answer. For
example:

2.005 g / 4.95 mL = 0.405 g/mL

 What is 16.874 x 2.6?

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3.2.4 : Significant figure & uncertainty

o What is 16.874 / 2.6?

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3.2.5 : Confidence limits & significance test

o Q-test : Deciding whether an outlying value (outliers) in a set of

replicate results should be RETAINED or REJECTED in
calculating the mean for the set of data.

o T-test : Determining the number of replicate measurements

required so that the experimental mean falls in the range where
expected true value lies.
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3.2.6 : Gross error & Q-test

ACCEPTING OR REJECTING AN EXPERIMENTAL DATA (Q-test)

o The method by which an experimental data can be rejected involves the use of a
statistical test.

o By using The Q-Test, it can indicate with a reasonable probability that a

particular value should be retained or rejected.
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3.2.6 : Gross error & Q-test
Steps involved in Q-test

1.Arrange the data in an increasing order.

2.Calculate the difference between the suspect value and its nearest neighbor,
(a).

3.Calculate the range (difference between highest and lowest values), (w).
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3.2.6 : Gross error & Q-test

4. Calculate , Q by using the following relationship.

a
5. Qexp =
w

6. Qexp is then compared to the Qtable. If the value of Qexp

 Qtable, the questionable result can be rejected with
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3.2.6 : Gross error & Q-test
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3.2.6 : Gross error & Q-test

Trial no. ? appears incorrect, check using Q-test at 90% confidence whether
trial ?????? should be rejected or accepted.

Trial I II III IV V VI VII

Volume 25.75 25.62 25.52 25.21 25.65 25.60 25.71
of HCl
used. (mL)
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3.2.6 : Gross error & Q-test
Solution:

25.21  25.52 0.31

= = 0.57
25.75  25.21 0.54

Q > Qcrit ie. 0.57 >0.51 , therefore the reading 25.21 should be rejected.

Example 3: The analysis of a city drinking water for arsenic yielded values of 5.60. 5.64, 5.70, 5.69,
and 5.81 ppm. The last value appears anomalous; should it be rejected at the 95% confidence level?
[Answer: not rejected, Q < Qcrit : 0.52 < 0.71]
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3.2.7 : t-Test

t-TEST
o The t-test assesses whether the means of two groups are statistically different from each other.

o This analysis is appropriate whenever you want to compare the means of two groups.

o Determining the number of replicate measurements required so that the experimental mean falls in the range where expected true
value lies (t-test).
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3.2.7 : t-Test

Probability/chances we called it RANGE.

RANGE which the true value falls (the highest - the lowest).

The range is called the confidence interval and the limit of this range is called the confidence limit.

confidence limit = ±
ts
x
here N
t = N-1(Degree of freedom from Table 1)
and N = number of trial
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3.2.7 : t-Test
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3.2.7 : t-Test
Example 4: During the standardization of HCl solution with 0.05 M Na2CO3 standard solution, the
burette readings obtained are shown in the table below:

Trial I II III IV V VI VII

Buret 25.75 25.62 25.52 25.21 25.65 25.60 25.71
Vol (mL)

The true known value is 25.63 mL.

o Calculate the standard deviation and the volume of HCl that can be reported at 90% confidence
level. [answer: 25.64  0.067]
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3.2.7 : t-Test
Example 5: A clinical chemist obtained the following data for the alcohol content of a sample of
blood: % C2H5OH: 0.084, 0.089, and 0.079. Calculate the 95% confidence interval for the mean.
[answer: 0.084  0.006]