Review Review

•Accuracy and Precision

•Systematic error and Random error •Mean; Median
•Sources of systematic error •Sample standard deviation
*Instrumental errors •Number of degree of freedom
*Method error •Standard error of a mean
*Personal errors •Pooled statistics
•Individual random error is usually small and •Propagation of error
undetectable
•Accumulation of these small error sources results
in random error for whole measurement
---follows Gaussian distribution (bell shape)

Significant Figures
Rules
• addition and subtraction
—identify common decimal point
• multiplication and division
—limited to the least number of
significant figures
• logs and antilogs
—limited to number of digits in
mantissa

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 Significant Figures Significant Figures
Sig Figs in Graphs • Data in the lab deals with numbers
100000
• Rules have been developed to express the error
associated with each number and the goodness of
80000
each number
60000

40000
Example: pan balance----error of 0.01 g
20000

0
0 .5 1 2 .5 5
• a 100.0000 g item that is weighed can only be
S h e a r R a t e ( rp m )
reported as 100.00 g
• digits beyond 100.00 are not significant
• Significance of data is described through
• data only has 5 significant figures
use of error bars

Reporting Computed Data

Rounding data
& Indicate the reliability of data
*Confidence limit: 90-95% confidence level *rounded to contain only significant digits
*Standard deviation *postpone the rounding until the calculation
is completed
& Consider significant figures
All of the certain digits and the first uncertain digit *at least a ‘guard’ digit need be carried
*Convention through the computation
*Computation rules
NO RELATIONSHIP between
& Rounding data
the number of significant figures
The computed results of a chemical analysis and the number of digits
must be rounded before being reported displayed on a calculator!!!!!

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 Statistical Data Treatment Statistical Data Treatment
Reading Ch7
Confidence Level (CL) z: probability factor
--Define an interval around an experimentally (the deviation from the mean in units of σ)
CL z zσ
determined mean that probably contains the CI = µ ±
population mean µ (probability that the true mean 50 0.67 N
lies in a certain interval) 68 1.00
80 1.29 •N is a very large number
•A common calculation to report variability of data
90 1.65 •Z comes from the infinity
•A quick way of identifying outlying values
95 1.96 row of the t value
Confidence Interval (CI):The range of values within 99.99995 5.00
which the population mean µ is expected to lie at
certain CL.
zσ For small data sets (much more common)
For large data sets CI = µ ± We can rely on the t test.
N

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 t Values
x−µ x−µ
t= vs z=
s σ
•Like z, t depends on the desired CL
•t values account for error introduced based on
sample size, degree of freedom and potential
sample skew. ts zσ
CI = x ± CI = µ ±
N N
s: standard deviation of the mean
•when N→∞, t→z. (Table 7-3)
•At the same desired CL, N↑, t↓

t Values ts Comparing Results

CL = x ±
Example N •The t-test is used to determine if two results are
Data: 1.00, 1.01, 1.02, 1.10, 0.95, Df =N-1 =4 statistically different
x
mean = 1.02 (round from 1.016) (1) comparing x with a true value (xt) (accuracy)
(2) comparing x1 with x2 (precision)
At df =4: 90% CL, t=2.13; 95% CL, t = 2.78
ts
N In form (1), x − xt = ±
∑ (x − x)
i
2
N
s= i =1
= 0.0541
N −1 If the x − xt is significantly larger than either the
2.13 × 0.0541 expected or the critical value, we may assume that
CI 90% = 1.016 ± = 1.02 ± 0.05(±5%)
5 this difference is real and the systematic error is
2.78 × 0.0541 significant.
CI 95% = 1.016 ± = 1.02 ± 0.07(±7%)
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 Comparing Results
More easier way to compare
x − xt
tcalc. =
s
If tcalc. > tcrit., then the difference is significant
Again, depending on the desired CL
Comparing two experimental means
Two sets of numbers
--- from different samples
N --- from different assays of the same sample
•They are actually different.
•If the means are identical, it is more likely an
accident than anything else.
To test if the two means actually differ, first
you must calculate the mean and standard
deviation for each set.

Comparing two experimental means We can also calculate t by

x1 − x2
Steps to follow tcalc. = N1 N 2 /( N1 + N 2 )
sp
1. Pool s values to obtain sp If tcalc. > tcrit., then the difference is significant
2. Calculate the variance of the mean for both sets.
s 12 = s 2p / N 1 , s 22 = s 2p / N 2 Example
3. Calculate the difference between the two means A--mean = 50 mg/L, s = 2.0 mg/L, N1 = 5
(s ) 2
/ N = s 12 + s 2
= s 2
/ N + s 2
/ N
d 2 p 1 p 2
B--mean = 45 mg/L, s = 1.5 mg/L, N2 =6
s d / N = s p (N 1 + N 2 ) N 1 N 2

x1 − x = ± ts (N + N ) N N
x1 − x 2 = 5 mg / L
2 p 1 2 1 2

4. Pick t based on desired confidence level and df Are the two sets of data significantly different at 95%
(df = nA + nB –2), If x 1 − x 2 > V crit . CL?
Then the means are different.

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Steps to follow The F test
The F test can be used to tell if the precision of two
1. s = 2 × 4 + 1.5 × 5 = 1.74
2 2

p
4+5 sets of measurement are different.
2. x1 − x 2 5 •Has the measurement precision changed?
t calc. = N 1 N 2 /( N 1 + N 2 ) = 5 × 6 /(5 + 6) = 4.74
sp 1.74
•Has the method been altered?
3. Use 95% confidence limit (t = 2.26) •Were there any significant changes due to the
lab or analyst?
tcalc. > tcrit .
Sl2arg er
So the means are different at the 95% confidential level. Calculation of F F = 2
S smaller
F ≥ 1 and depends on the confidence level and df.
NOTE: if t calc . < t crit . , it does not mean that two
You can look up the Fc value for the desired levels
means are equal,it means no significant difference
(Table 7-4).

The F test
Example
A-- s = 0.15 ppm, df =12
B-- s = 0.12 ppm, df =20

F = 0.152/0.122 = 1.56
Fc is 2.28 at 95% confidence.
F < Fc, one cannot say method A is better than
method B in terms of the precision

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 Rejection of data Q test
Sometimes we know that a data point looks Assumes
bad(outlier).
• x and Sx are unknown.
Outliers
• Data is normally distributed.

We can’t just pitch it out---there must be a basis Steps to reject data

for rejection data. 1.Rank the data: x1 < x2 < … < xm
Methods for Rejecting data 2.Choose confidence level
•Dixon test---Q test 3.Calculate ratio (based on n) Qexp = xq − xn / W
•Rule of the huge error
•Grubbers test 4.Look up proper value
Each has its own advantages/disadvantages. 5.If ratio > table value then reject (Table 7-5)

Q test
Example: The analysis of a calcite sample yielded
CaO percentages of 55.95, 56.04, 56.08, 56.23, and
56.00. The values of 56.23 appears anomalous, should
it be rejected at the 95% confidence level?

1.Rank the data: 55.95, 56.00, 56.04, 56.08, 56.23

2. Confidence level: 95%
3.Calculate ratio (based on n)
Qexp = xq − xn / W = (56.23 − 56.08) /(56.23 − 55.95) = 0.54
4.Look up proper value (Qcrit = 0.71 at 95% CL)
5. 0.54 < 0.71, then retain the outlier at 95% CL.

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 Standardization and Calibration
•Instruments and techniques produce signals, not
concentrations.
•Analyst must correlate the signal level to a
corresponding concentration---Calibration.
•The working curve is produced through regression
analysis to find best fit
1. Comparison with Standards
2. External Standard Calibration
Method of Least Squares
•Assuming there is a linear relationship between the
measured variable (y) and the analyte conc. (x)
y = mx + b
• Assuming that any deviation of individual points
from the straight line is from the error of
measurement
In other words, no error from x value (knowing the
exact conc. of standard samples)

Regression Analysis
Residual = yi-(mxi+b) For the linear equation:
y = mx + b
Useful quantities:

Least squares method:

minimize the sum of the
squares of the residuals
from all data points

Slope:
Intercept:

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 Regression Analysis Example

Standard deviation of the residuals:

Standard deviation of the intercept:

Standard deviation of the slope:

Standard deviation of a unknown read from a
calibration curve:
Sxx = 6.90201 - (5.365)2/5 = 1.14537
N--the number of calibration data points. Syy = 36.3775 - (12.51)2/5 = 5.07748
L--the number of replicate measurements of unknown. Sxy = 15.81992 – 5.365 × 12.51/5 = 2.39669
and yc is the mean of the unknown measurements.

Then we can calculate Quality assurance and control chart

m= Sxy / Sxx = 2.39669/1.14357 = 2.09 Quality Assurance
b = y − mx = 12.51/ 5 − 2.0925× (5.365/ 5) = 0.26 A series of activities to provide the producer/user
And the equation for the least-squares line of a product the assurance that it meets the needs
of users
y = 2.09x + 0.26
Further calculations lead to Importance
5.07748 − (2.095) × 1.14537
2
•Clinical diagnosis
sy = = 0.144 = 0.14
5−2 •Environmental protection
s y2 •Food safety
sm = = 0.144 2 / 1.14537 = 0.13
s xx •Reliability of scientific studies
1 •…
sb = 0.144 = 0.16
5 − (5.365) 2 / 6.90201

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 Quality assurance and control chart Quality Control Chart
--Define the upper control limit(UCL) and the lower
Two types of quality assessment measurements
control limit(LCL)
*Evaluation of the accuracy and precision of the 3σ 3σ
UCL = µ + LCL = µ −
methods of measurement N N
*Evaluation of product quality (e.g., F in toothpaste)
µ----population mean for the mass measurement
How to assess the quality σ----population standard deviation
---usage of quality control chart
N----the number of replicates

Example: control chart for a analytical balance Example: Control chart for monitoring the conc.
of benzoyl peroxide in a commerical product

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