Data Handling in Analytical

Chemistry
 Why do we need statistics in
analytical chemistry?
• Scientists need a standard format to
communicate significance of experimental
numerical data.
• Objective mathematical data analysis
methods needed to get the most information
from finite data sets
• To provide a basis for optimal experimental
design.
 What Does Statistics Involve?
• Defining properties of probability
distributions for infinite populations
• Application of these properties to
treatment of finite (real-world) data sets
• Probabilistic approaches to:
– Reporting data
– Data treatment
– Finite sampling
– Experimental design
 Some Useful Statistics Terms
• Mean – Average of a set of values
• Median – Mid-point of a set of values.
• Population – A collection of an infinite munber of
measurements. N  infinity
• Sample – A finite set of measurements which
represent the population.
• True value (true mean)- (m), mean value for the
population.
• Observed Mean –(x), mean value of the sample set
 Determinate Errors
Are They Systematic?
• Determinate Errors:
• Determinable and either avoided or
corrected.
• Constant errors
• Uncalibrated weights
• Burets- volume readings can be corrected
• Concentration variation with temperature
 Indeterminate Errors
Are They Random?
• Indeterminate Errors-
– accidental or random errors
• Represent the experimental uncertainty that
occurs in any measurement.
– Small difference on successive measurements
• Random Distribution
• Mathematical Laws of Probability
• Normal distribution or Gaussian Curve
 THE GAUSSIAN DISTRIBUTION
Probability

- Range of measurements for ideal Gaussian distribution

- The percentage of measurements lying within the given range
(one, two, or three standard deviation on either side of the mean)

Range Gaussian Distribution (%)

µ ± 1σ 68.3
µ ± 2σ 95.5
µ ± 3σ 99.7
Random errors follow a Gaussian or normal distribution.
We are 95% certain that the true value falls within 2σ (infinite population),
IF there is no systematic error.

©Gary Christian,
Analytical Chemistry,
6th Ed. (Wiley) Fig. 3.2 Normal error curve.
 Ways of Expressing Accuracy
• Absolute Errors: difference between true
value and measured value
• Mean Errors: difference between true
value and mean value
• Relative Error: Absolute or Mean Errors
expressed as a percentage of the true value

((m-x)/m)*100 = % Relative Error

 THE GAUSSIAN DISTRIBUTION
Arithmetic Mean

- Also known as the average

- Is the sum of the measured values divided by the number
of measurements

_ x i
= (x 1  x 2  x 3  .....  x n )
1
x = i
n n
∑ = sigma, symbol for the sum
xi = a measured value
n = number of measurements
 THE GAUSSIAN DISTRIBUTION
Standard Deviation

- A measure of the width of the distribution

- Small standard deviation gives narrow distribution curve

2
  _

  xi  x 
i  
s =
n 1
xi = a measured value
n = number of measurements
n-1 = the degrees of freedom
Standard deviation has the same number of decimal places as the mean
THE GAUSSIAN DISTRIBUTION

Relative Standard Deviation

s
Relative Standard Deviation = _
x 100
x

- The sample mean and sample standard deviation

(x and s) apply to finite set of measurements

- For infinite set of data use is made of the true

mean or population mean (designated µ) and
the true standard deviation (designated σ)
THE GAUSSIAN DISTRIBUTION

Variance

- Is the square of the standard deviation

- Variance = σ2
THE GAUSSIAN DISTRIBUTION

Median

- The middle number in a series of measurements

arranged in increasing order

- The average of the two middle numbers if the

number of measurements is even
 THE GAUSSIAN DISTRIBUTION

Mode

- The value that occurs the most frequently

Range

- The difference between the highest and the lowest values

All but the range should be expressed with one

extra digit beyond the last significant digit
 Confidence Limit (Confidence Interval)
How sure are you?
_
ts
μ = x
n
- That is, the range of confidence interval is
– ts/√n below the mean and + ts/√n above the mean

- For better precision reduce confidence interval by increasing

number of measurements
 CONFIDENCE INTERVAL

t statistical factor that depends on the number

of degrees of freedom
 degrees of freedom = N-1

Values of t at different confidence levels and

degrees of freedom are located in table
Select a confidence level (95% is good) for the number of samples analyzed
(= degrees of freedom +1).
Confidence limit = x ± ts/√N.
It depends on the precision, s, and the confidence level you select.

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

 Confidence Interval
• Seven measurement of the pH of a buffer
solution gave the following results:
5.12 , 5.20, 5.15, 5.17, 5.16, 5.19, 5.15

Calculate the 95% and 99% confidence limits of

the true pH