SAMPLING

Fundamental Statistical Terminologies

A measurement is considered to be accurate if the difference between the measured value and the true value falls within an acceptable margin. How do we know the true value? We rely on statistics therefore.

A random error (or variation) on average, over a period of time, tend to zero whereas integrated systematic errors result in a net positive or negative value

 The bias is the difference between the true value and the average of a number of experimental values and hence is the same as the systematic error. The variance between repeated samples is a measure of precision or reproducibility. The difference between the mean of a series of repeat samples and the true value is a measure of accuracy

Mode and median are measures of the central value of a distribution. The mode forms the peak of the frequency distribution, while the median divides the total number of measurements into two equal sets of data. If the frequency distribution is symmetrical, then its mean, mode and median coincide.

Symmetrical Distribution

Asymmetrical Distribution

The variance, and its derived parameters such as the standard deviation and the coefficient of variation, are the most important measures for variability between test results. The classical formula for the calculation of the variance is:

where n = number of measurements n-l = degrees of freedom The standard deviation, a, is the square root of the variance.

Another important term is confidence interval

What is Sampling ?
Procedure by which some members of a population are selected as representative of the entire population The sub-group thus selected to represent the whole population is known as SAMPLE

Methods Of Sampling
Several methods are used to ascertain a particular aspect of the population, through an unbiased sample drawn from the population Sampling is divided in two categories 1. Probability Sampling 2. Non-probability Sampling

Probability sampling
It is any method of sampling that utilizes some form of random selection The procedure should assure that the different units in the population have equal probabilities of being chosen.

Non probability sampling

It does not involve random selection May or may not represent the population well Used when researcher lacks a sampling frame for the population

Probability sampling
Includes: Simple Random Method Systematic Sampling Stratified Sampling Cluster Sampling Multistage Sampling

Nonprobability Sampling
Includes : Accidental Sampling Voluntary Sampling Purposive Sampling Quota Sampling

Importance of Sampling in Metallurgical Accounting

LOT Primary Secondary Analysis Result sample sample

m
(s)

s1

s2

s3

sx
x

Propagation of errors: s x

2 s i

Example: sx (5%)2 (2%)2 (1%)2 30(%)2 5.5% GOAL: x = m Analytical process usually contains several sampling and sample preparation steps

Global Estimation Error GEE

Total Sampling Error TSE
Point Materialization Error

Total Analytical Error TAE

Weighting Error

PME
Increment Delimitation Error Increment Extraction Error

SWE
Increment and Sample Preparation Error

IDE

IXE
Point Selection Error

IPE PSE

Long Range Point Selection Error

Periodic Point Selection Error

PSE1
Fundamental Sampling Error Grouping and Segregation Error

PSE2

FSE

GSE

GEE=TSE +TAE TSE= (PSE+FSE+GSE)+(IDE+IXE+IPE)+SWE

Error components of analytical determination according to P.Gy

Weighting error
Sample No. 1 2 3 4 5 6 7 8 9

Concentration mg/l
6.25 4.36 5.58 4.64 4.86 3.65 3.73 5.98 4.96

Volume 3 m
4.58 3.71 5.20 5.71 4 .54 6.78 7.12 5.81 5.86

cV g
28.6 16.2 28.99 26.48 22.08 24.75 26.55 34.76 29.05

Mean Sum

4.89 44.01

5.479 49.3

26.39 237.47

Vi Total emission estimate (unweighted):

3 3 M 9 c V 9 4 .89 g / m 5 .479 m

Weighted mean concentration:

ciVi

= 4.86 mg/l

241.13

M w 9 c w V 9 4 .86 g / m 3 5 .479 m 3

Total emission estimate (weighted):

237.47 g

Weighting error (in concentration): 0.03 mg/l

Weighting error (in total emission): 3.66 g

Sample delimitation

Incorrect

Correct

v = constant 0.6 m/s

if d > 3 mm, b 3d = b0 if d < 3 mm, b 10 mm = b0 a b c

v d = diameter of largest particles b0 = minimum opening of the sample cutter

Correct design for proportional sampler:

correct increment extraction

Incorrect Increment and Sample Preparation

Errors
Contamination (extraneous material in sample) Losses (adsorption, condensation, precipitation, etc.) Alteration of chemical composition (preservation) Alteration of physical composition (agglomeration, breaking of particles, moisture, etc.) Involuntary mistakes (mixed sample numbers, lack of knowledge, negligence) Deliberate faults (salting of gold ores, deliberate errors in increment delimitation, forgery, etc.)

Estimation of Fundamental Sampling Error by Using Poisson Distribution

Poisson distribution describes the random distribution of rare events in a given interval. If mn is the number of critical particles in sample, the relative standard deviation expressed as the number of particles is

sr

mn

Example
Plant Manager: I am producing fine-ground limestone that is used in paper mills for coating printing paper. According to their specification my product must not contain more than 5 particles/tonne particles larger than 5 mm. How should I sample my product?
Sampling Expert: That is a bit too general a question. Lets first define our goal. Would 20 % relative standard deviation for the coarse particles be sufficient? Plant Manager: Yes. Sampling Expert: Well, lets consider the problem. We could use the Poisson distribution to estimate the required sample size. Lets see:

The maximum relative standard deviation sr = 20 % = 0.2. From equation 2 we can estimate how many coarse particles there should be in the sample to have this standard deviation

1 1 n 2 25 2 s r 0.2
If 1 tonne contains 5 coarse particles this result means that the primary sample should be 25 tonnes. This is a good example of an impossible sampling problem. Even though you could take a 25 tonne sample there is no feasible technology to separate and count the coarse particles from it. You shouldnt try the traditional analytical approach in controlling the quality of your product. Instead, if the specification is really sensible, you forget the particle size analyzers and maintain the quality of your product by process technological means, that is, you take care that all equipment are regularly serviced and their high performance maintained to guarantee the product quality. Plant Manager: Thank you

d f= 1

d f= 0,524

d f= 0,5

d f= 0,1

default in most cases

l = (L/d)0.5

l=1

Limitations of Gys Equation

l C = f.g.l.m = 0.5*0.25*0.4*19.3 = 0.97

l = 0.4

Example 2

PLANNING OF SAMPLING
1. GATHERING OF INFORMATION

What are the analytes to be determined? What kind of estimates are needed? Average (hour, day, shift, batch, shipment, etc.) Distribution (heterogeneity) of the determinand in the lot Highest or lowest values Is there available useful a priory information (variance estimates, unit costs)? Is all the necessary personnel and equipment available? What is the maximum cost or uncertainty level of the investigation?

PLANNING OF SAMPLING
2. DECISIONS TO BE MADE Manual vs. automatic sampling Sampling frequency Sample sizes Sampling locations Individual vs. composite samples Sampling strategy Random selection Stratified random selection Systematic stratified selection Training

Plant Sampling Moving Stream

Incorrect Sampling
All these do not collect samples from the full stream

Reverse Spoon Cutter Incorrect because of Preferential Losses of Coarse Particles

Sampling of smelter products, residues and wastes

Sampling from Stationary Situations Sampling from Stockpiles

Sampling from the side of a stockpile will not provide a representative sample

Sampling from Ships, Trucks and Wagons

Moisture Sampling

Substantial moisture loss can occur when primary increments are conveyed to the secondary cutter on small open conveyors in sample stations

Moisture loss can occur when samples are stored in containers for long periods prior to being taken back to the laboratory for moisture determination

Laboratory Sampling
Grab Sampling

Step 1

Step 2

Coning and Quartering

Sample Splitters

Rotary Riffle

SUMMARY

ISO 13909-2 Guideline for Coal & Coke Samples

Thanks