Propagation of error

What is the density of the cube?

Measure the height, width,
length, and mass of the cube
Calculate the density r using
this formula

Single measurements

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Why Do Measurements Vary?
Every measurement is influenced by a
multitude of quantities that are not under
our control and of which we may not even
be aware (influence quantities)
 Random effects
Measurements also vary because the
measurand is not and cannot be specified in
infinite detail
 For example, I did not specify how the linear
measurements of the cube should be made
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Types of Errors
Random errors result from random effects in the
measurement
 the magnitude and sign of a random error changes
from measurement to measurement
 measurements cannot be corrected for random errors
 …but random errors can be quantified and reduced

Systematic errors result from systematic effects

in the measurement
 the magnitude and sign of a systematic error is
constant from measurement to measurement
 measurements can be corrected for known systematic
errors
 …but the correction introduces additional random errors
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Repeated Measurements

Sample Mean

5
 Repeated Measurements

Sample mean
sample standard
6
deviation
Uncertainty in Density
We have calculated the standard
uncertainty in the input quantities (length,
mass, etc)
How do we get the standard uncertainty in
the output quantity (density)?
 the combined standard uncertainty
Propagation of uncertainty

7
Propagation of error

  is the derived stdev

  is the stdev of a
  is the stdev of b
  is the stdev of c

8
Linear least squares fits
In some of the experiments in Physical
Measurements you will be asked to
draw the “best fit” line through a set of
data points
In the case of constructing a standard
or calibration curve, this line will
represent a fit to a linear equation
y = mx + b (m=slope, y=intercept)
Linear least-squares fit
In fitting the best
straight line to the data
we will use a method
called a linear least-
squares fit
The method assumes
Standard deviations
in y are greater than
in x data
Standard deviations
in y data are about the
same for all data
points
Linear least-squares fit
In order to carry the
method out we will
Minimize the deviations
between the y-data
points and the line
This requires that points
having positive
deviations are about
equal to points having
negative deviations
The deviations
di = (yi-y) = (yi – (mx+b))
 Real Data

The first two columns are the (x,y) points of data

The next two columns show xiyi and xi2
At the bottom of each column, we find the sums
Finding the best fit line

y = mx + b, using the determinant of matrix

 Finding error in slope and
intercept

Column 5 shows the difference between the best fit line and
each y data point. This is the residual.
The last column shows the square of the residuals. The
method of least squares minimizes the sum of the residual
squares.
Finding error in slope and
intercept
We can find the standard deviation in
the y data points according to
Standard deviation in y data

Standard deviation in slope

Standard deviation in intercept

Spreadsheet
There is a fair amount of number crunching
to do in calculating a best fit line
Your hand calculator may give you the best fit
slope and intercept but will not give you the
errors in slope and intercept
We will require errors in your lab reports
We will provide you with an Excel
spreadsheet which will give you the error in x
extrapolated from a “read” y value
Constructing a standard curve
In order to determine the concentration of
an unknown, we first construct a standard
curve with analytes of known concentrations
called standard solutions
For example, assuming Beer’s Law
A = ebc
We can plot absorbance vs concentration and fit
the data with a least squares best fit line
Constructing a standard curve
Before fitting the data it is
important to eliminate
questionable data points
which don’t seem to fit the
linear equation
y = mx + b
Notice also that in this case
the line does not pass
through the origin
 Constructing a standard curve
If Beer’s Law is correct the
line should pass through the
origin
A=ebc (notice intercept =
0)
One may force the line
through the origin by
subtracting the absorbance
of a blank from each y data
point
A blank is a solution which
Corrected absorbance is the
contains all the reagents but
absorbance minus the blank
no deliberately added analyte
Measuring your unknown
concentration
Once you have corrected absorbances,
do a linear-least-squares fit to the data
to obtain slope, m, intercept, b, and
errors in slope and intercept, sm and sb
Your data now allows you to take an
unknown and find its concentration,
knowing its absorbance
Measuring your unknown
concentration
From your best fit
A’sample = m[c] + b
[c] = (A’sample – b)/m
Where A’sample is the
corrected absorbance
A’sample = Asample – Ablank
Errors in your calculated
concentration
Because there is error in slope and intercept of the
best fit line, there is also an error in the calculated
concentration of your unknown.

For an unknown of calculated concentration [c]

which was measured k times. The remaining
parameters in the equation are from the best fit line.