Definition of measurement

uncer tainty

“A parameter associated with

the result of a measurement,
that characterizes the
dispersion of the values that
could reasonably be attributed
to the measurand”

Guide to the expression of

Uncertainty in Measurement.
ISO, Geneva (1993).
 Definition of measurement
uncer tainty

Which of the following volumetric glassware would give you the

most precise value?
Which of the following volumetric glassware would have the least
measurement uncertainty?
 T he impor tance of estimating
uncer tainties

ISO 17025

A calibration laboratory, or a testing laboratory performing its

own calibrations, shall have and shall apply a procedure to
estimate the uncertainty of measurement for all calibrations
and type of calibrations. (Sec 5.4.6.1)

In these cases the laboratory shall at least attempt to identify

all the components of uncertainty and make a reasonable
estimation, and shall ensure that the form of reporting of the
result does not give a wrong impression of the uncertainty. (Sec
5.4.6.2)
 The importance of estimating
uncertainties

Whenever decisions are based on analytical results, it is

important to have some indication of the quality of the results,
that is, the extent to which they can be relied on for the
purpose in hand.

Uncertainty of measurement does not imply doubt about

the validity of a measurement; on the contrary, knowledge of
the uncertainty implies increased confidence in the validity of a
measurement result. (QUAM 2.1.4)
 Error and uncertainty

It is important to distinguish between error and uncertainty.

Error is defined as the difference between an individual result

and the true value of the measurand.
As such, error is a single value. In principle, the value of a
known error can be applied as a correction to the result.
(QUAM 2.4.1)
Uncertainty, on the other hand, takes the
form of a range, and, if estimated for an
analytical procedure and defined sample
type, may apply to all determinations so
described. In general, the value of the
uncertainty cannot be used to correct a
measurement result. (QUAM 2.4.2)
 Error and uncertainty

To illustrate further the difference,

the result of an analysis after
correction may by chance be very
close to the value of the measurand,
and hence have a negligible error.
However, the uncertainty may still
be very large, simply because the
analyst is very unsure of how close
that result is to the value. (QUAM
2.4.3)
The uncertainty of the result of a
measurement should never be
interpreted as representing the error
itself, nor the error remaining after
correction. (QUAM 2.4.4)
 Definition of measurement
uncer tainty

NOTE 1 The parameter may be, for example, a standard

deviation [B.20] (or a given multiple of it), or the width of a
confidence interval.

B.20 Sample Standard Deviation

s - an estimate of the population standard deviation σ from a
sample of n results.
Po o l e d s t a n d a r d d e v i a t i o n
( S pooled)
 A b s o l u t e a n d R e l a t i ve U n c e r t a i n t y

Absolute Uncertainty expresses the margin of uncertainty

associated with a measurement.
Example. If the estimated uncertainty in reading a
calibrated buret is ± 0.02 mL, we say that ± 0.02 mL is the
absolute uncertainty associated with the reading.
Relative Uncertainty compares the size of the absolute
uncertainty with the size of its associated measurement.
Example. The relative uncertainty of a buret reading of
12.35 mL ± 0.02 mL is a dimensionless quotient:
𝒂𝒃𝒔𝒐𝒍𝒖𝒕𝒆 𝒖𝒏𝒄𝒆𝒓𝒕𝒂𝒊𝒏𝒕𝒚
𝑹𝒆𝒍𝒂𝒕𝒊𝒗𝒆 𝑼𝒏𝒄𝒆𝒓𝒕𝒂𝒊𝒏𝒕𝒚 =
𝒎𝒂𝒈𝒏𝒊𝒕𝒖𝒅𝒆 𝒐𝒇 𝒎𝒆𝒂𝒔𝒖𝒓𝒆𝒎𝒆𝒏𝒕

= 0.02 mL / 12.35 mL = 0.002

 Percent Relative Uncertainty

The percent relative uncertainty is simply:

𝑷𝒆𝒓𝒄𝒆𝒏𝒕 𝑹𝒆𝒍𝒂𝒕𝒊𝒗𝒆 𝑼𝒏𝒄𝒆𝒓𝒕𝒂𝒊𝒏𝒕𝒚 = 𝟏𝟎𝟎 𝒙 𝑹𝒆𝒍𝒂𝒕𝒊𝒗𝒆 𝑼𝒏𝒄𝒆𝒓𝒕𝒂𝒊𝒏𝒕𝒚

If the absolute uncertainty in reading a buret is constant ± 0.02 mL,

the percent relative uncertainty is 0.2 %.
 Law of Pr opagation of
Uncer tainty

Addition and Subtraction

For a measurement result y, the total uncertainty, termed
combined standard uncertainty and denoted by uc(y), is an
estimated standard deviation equal to the positive square root of
the total variance obtained by combining all the uncertainty
components.
𝑝 ±𝑢 𝑝
+ 𝑞 ±𝑢 𝑞
𝑟 ±𝑢 𝑟
𝑦 ± 𝑢𝑐 𝑦
 Law of Pr opagation of Uncer tainty

Sample Exercise:
Find the absolute and percent relative uncertainty and express
each answer with a reasonable number of significant figures.
9.23 ( ± 0.03) + 4.21 ( ± 0.02) - 3.26 ( ± 0.06) = ?
Answer:
10.18 ± √ (0.03)2 + (0.02)2 + (0.06)2
10.18 ± 0.07 (absolute uncertainty)
10.18 ± 0.69% (percent relative uncertainty)
Rule for significant figures:
The first uncertain figure of the answer is the last significant
figure.
Law of Pr opagation of Uncer tainty

Multiplication and Division

𝑝 ±𝑢 𝑝 𝑥 𝑞 ±𝑢 𝑞
= 𝑦 ± 𝑢𝑐 𝑦
𝑟 ±𝑢 𝑟
 Law of Pr opagation of
Uncer tainty

Sample Exercise:
Find the absolute and percent relative uncertainty and express
each answer with a reasonable number of significant figures.
91.3 ( ± 1.0) x 40.3 ( ± 0.2)
21.1 ( ± 0.2)

2 2 2
1.0 0.2 0.2
174 ± + +
91.3 40.3 21.1

174 ± 0.015 (relative uncertainty)

174 ± 2 % (percent relative uncertainty)
174 ± 3 (absolute uncertainty)
 Law of Pr opagation of Uncer tainty

Mixed Operation
Find the absolute and percent relative uncertainty and express
each answer with a reasonable number of significant figures.
6.2 ± 0.2 − 4.1 (± 0.1)
Apply Rule #1 for the numerator
9.43 (± 0.05)

2.1 ± 0.2 2 + (0.1)2

9.43 (± 0.05)

2.1 ± 0.22
Apply Rule #2
9.43 (± 0.05)
 Law of Pr opagation of
Uncer tainty

2 2
0.22 0.05
0.22 ± +
2.1 9.43

0.22 ± 0.10 (relative uncertainty)

0.22 ± 11% (percent relative uncertainty)
0.22 ± 0.02 (absolute uncertainty)
 Assignment

The standard deviation in measuring the

diameter (d) of a spherical metal is ± 0.02 cm.
What is the standard deviation in the calculated
volume (V) of the sphere if d = 2.15 cm?
The weight of the spherical metal was
determined as follows:
Weight of small beaker = 25.75 grams
Weight of small beaker + metal sphere = 39.80 grams
The uncertainty in weighing is ± 0.05
grams. What is the standard deviation in the
weight determination of the metal sphere?
What is the uncertainty in the density
measurement? Calculate the %RSD in the
density measurement.