WELCOME

WELCOME
 KUVEMPU UNIVERSITY
SIR MV GOVERNMENT SCIENCE COLLEGE
BOMMANAKATTE-BHADRAVATHI
A SEMINAR TOPIC ON:
“EVOLUTION OF ANALYTICAL DATA”

SUBMITTED TO,
THE CHAIRMAN,
DEPARTMENT OF P.G STUDIES INDUSTRIAL CHEMISTRY,
M.Sc.,(INDUSTRIAL CHEMISTRY).
SUBMITTED BY,
AISHWARYA S M
1st MSC-IC
P06VS22S086003
Contents

 Introduction
 Statistical treatment of finite sample reliability of result
 Calculation of fundamental statical paramters
 Least Square Method
 Curve fitting method
 Criteria for rejection of an observation
 Q,F and T test for comparison of results
Introduction
 Laboratory that performs analysis providing a basis for utility must have a
quality assurance programme .
 When accessing certain analytical data we are generally interested must in
learning that up to what extent the result.
 Statistical calculations are necessary to understand the significance of the
data that are collected .
 The role of statistical calculations is to sharpen the analytical judgment
concentrating the effects of intermediate errors.
 We can use statistical method to evaluate the random errors which follow a
normal distribution or Gaussian distribution.
Statistical treatment of finite sample
reliability of results
 MEAN:- It is average of series of results .It may be calculated by taking the
average of individual results as shown below

 MEDIAN:- The median of an even number of results is nothing but the average
of two middle values provided the results are listed in order;
whereas for an odd number of results the median is the middle value itself.
 Median is an useful measure specifically when dealing with small samples .
 Average Deviation( Mean Deviation):- It’s the average of the differences
between the individual results and the mean . It is regarded as measure of
variability.
 Standard Deviation:- It is the distance from the mean to the point of
inflexion of the normal distribution curve. For a finite number of values it is
normally symbolised as ‘s’ and may be regarded as follows:

 Coefficient of variation(V):- It is simply the standard deviation expressed as a

percentage of mean(x) as stated below:

 Variance :- The variance is the square of the standard deviation.

However ,the former is fundamentally more important in statistics than the
latter, whereas the latter in employed more frequently in the treatment of
chemical data.
Calculation of fundamental statistical parameters.

 The normality of solution of sodium hydroxide as determined by an analyst by

four different titrations are found be 0.5038;0.5049,0.5040 and 0.5039.
Calculate the mean ;median ;average deviation ;standard deviation and
coefficient of variation .
Least Square Method
 The least square method is a form of mathematical regression analysis used to
determine the line of best fit for a set of data providing visual demonstration
of the relationship between data points.
 The LSM is standard approach in regression analysis to approximate the
solution of overdetermined system by minimizing the sum of squares of the
residual made in the result of every single equation.
 Curve fitting method:-
1) Find the curve of best fit y= for the following data by using the method of
least square.

X 1 5 7 9 12
Y 10 15 12 15 21
 Sol:-
y=
taking log on both sides
logy=loga +
Y=A+Bx
=nA+B
=A + B

x y Y=logy

1 10 1 1 1
5 15 1.18 25 5.9
7 12 1.08 49 7.56
9 15 1.18 81 10.62
12 21 1.32 144 15.84
=34 =5.76 =300 =40.92
5.76=5A+B.34
40.92=34.A+300.B
A=1 or 0.98
B=0.025 =>log b=B
log a=A =>b=antilog(B)
=1.06
a=antilog(A)
a=9.55
y=
y=9.55
Criteria for rejection of an observation

 Unlabelled or mislabelled samples

 Duplicate sample , most duplicate samples received on the same day are
unacceptable and should not be processed
 Contaminated samples
 Leak containers
 In appropriate sample sources.
 F test:- (Variance ratio test)
 The test based on the test statistic which follows F distribution is called F-
test .
 The significant difference between variance of two population based on
small examples drawn from those population
F= /
 In the F-ratio use always take the larger of the two estimates in the
numeration and smaller in denominator
 The degree of freedom is (n1-1) & (n2-1)
Application :-
 The test assumption of equal variances that was made in using the F-test
 Intersect in actually comparing the variances two populations
Distribution:-
Assume we repeatedly select a random sample of from two normal population
Consider the distribution of the ratio two variances
F=
The distribution formed in thin manner approximates on F–distribution with the
following degree of freedom
v1=n1-1 & v2=n22
Eg:-Assume that we have two samples with
n2=7 & n1=10
df=7-1=6 & df=10-1=9
Let v=F(6,9)
where 6 is the df from numerator and 9 is the df of the denominator.
 Q test:-
It is a statistical test for deciding if an outlier can be removed from a set of data.
It is used for small data sets.
Q= gap/range
gap – nearest value
Range-lowest value
Reject outlier of Qcal>Qtab
 Procedure:-
1) Calculate the range
2) Calculate the difference between the extreme value with nearest neighbours.
3) Calculate the ratio(Q-value) between the difference and the range.
Ex:- Consider the set of data : Q-value in several sample:-v
9.52,10.7,13.1,9.71,10.3,9.99 mg/L
Arrange data in increasing or decreasing order
9.52,9.71,9.99,10.3,10.7,13.1
The questionable data point is 13.1
Calculate Qcal=gap/Range = (13.1-10.7)/(13.1-9.52) = 0.670
If Q>Qtable where Qtable is a reference value corresponding to the sample side
and confidence level, then reject the questionable point
20.52,16.34,13.84,18.44,15.44,19.33

 T Test:-
One uses this test when the population variance is unknown as is usually the case
in the social science .
The standard errors the sampling distribution of the sample mean is estimated.
A t-distribution is used to create confident intervals like critical values.
 T-distribution:-
A very to the z-distribution by assuming normality is obtained after about 100
data observation
 Basic rule of parameter estimation
The higher the n number of sample the more reflecting of overall
population.
Formula:- t=(x-µ)/ (σ/
where ‘x’ bar is the mean of the sample
µ is the assumed mean ,
σ is the standard deviation ,
n is the number of observations
Reference

 Basic concepts of analytical chemistry –

S.M KHOPKAR
 Fundamentals of Analytical chemistry-
Doughlas A Skoog.
Thank You