Chapter 3

Experimental Error

The derailment on October 22, 1895 of

the Granville-Paris Express that overran
the buffer stop. The engine careened
across almost 100 feet (30 meters) of
the station concourse, crashed through
a two-foot thick wall, shot across a
terrace and sailed out of the station,
plummeting onto the Place de Rennes
30 feet (10 meters) below where it
stood on its nose. While all of the
passengers on board the train survived,
one woman on the street below was
killed by the falling train.
 Significant Figures
• ”The number of significant figures is the minimum
number of digits needed to write a given value in scientific
notation without loss of accuracy.“

9.25 x 104 3 signif. figs

9.250 x 1044 signif. figs
9.2500 x 104 5 signif. figs

• most significant figure - the left-hand most digit, the digit

which is known most exactly

• least significant figure - the right-hand most digit, the digit

which is known most exactly
 Counting Significant Figures

Rules for determining which digits are significant:

1. All non-zero numbers are significant.

2. Zeros between non-zero numbers are significant.

3. Zeros to the right of the non-zero number and to

the right of the decimal point are significant.

4. Zeros before non-zero numbers are not significant.

 Significant Figures

When reading the scale of any apparatus, you

should interpolate between the markings. It is
usually possible to estimate to the nearest tenth
of the distance between two marks.

0. 55 cm?
0. 56 cm?
2 signif. figs

0 1 cm
0. 55 cm implies an error of at least 0.55 ± 0.01 cm
 Significant Figures

In experimental data, the first uncertain

figure is the last significant figure.
 Significant Figures in Arithmetic
Exact numbers
conversion factors, significant figure rules do not
apply
 Significant Figures in Arithmetic
Addition and Subtraction
For addition and subtraction, the number of
significant figures is determined by the piece of
data with the fewest number of decimal places.

4.371
+ 302.5
306.8
 Significant Figures in Arithmetic
•  
Multiplication and Division
For multiplication and division, the number of
significant figures used in the answer is the
number in the value with the fewest significant
figures.
 Significant Figures in Arithmetic
Logarithms and Antilogarithms
logarithm of n:
n = 10a log n = a
n is the antilogarithm of a
log (339)= 2.530 log(3.39 x 10-5 )=-4.470
2 character -4 character
.530 mantissa .470 mantissa
 Significant Figures in Arithmetic
Logarithms and Antilogarithms
The number of significant figures in the mantissa
of the logarithm of the number should equal the
number of significant figures in the number.

The character in the logarithm corresponds to the

exponent of the number written in scientific
notation.
 Significant Figures in Arithmetic
Logarithms and Antilogarithms
The number of significant figures in the
antilogarithm should equal the number of digits
in the mantissa.

antilog (-3.42) = 10-3.42 = 3.8 X 10-4

2 s.f. 2 s.f. 2 s.f.

 Significant Figures in Arithmetic
• n = 1 x 102 (1 s.f.), log(2.0) (1s.f)
• n = 5 x 102 (1 s.f.), log(2.7) (1s.f)
• n = 1 x 103 (1 s.f.), log(3.0) (1s.f)
 Types of Error
Systematic Error (determinate error)
• The key feature of systematic error is that, with
care and cleverness, you can detect and correct it.

• Examples of Determinate Errors

instrument error
method errors
personal errors
 Analog Spectrometer

% T = 58.5 ? A = 0.233 ?
0.003  𝐀=−𝐥𝐨𝐠 ⁡(𝐓 ) 0.001
= 58.3 ? = 0.234 ?
% T = 18.5 ? A = 0.733 ?
0.003  𝐀=−𝐥𝐨𝐠 ⁡(𝐓 ) = 0.738 ?
0.005
= 18.3 ?
 Types of Error
Effects of Determinate Errors
constant errors

Detection of Determinate Instrument and Personal

Errors
 Types of Error
Detection of Determinate Method Errors
analysis of standard samples (SRS)
independent analysis
blank determinations
variation in sample size
(SRS) Standard Reference Samples
 Types of Error

Detection of Determinate Method Errors

• analysis of standard samples (SRS)

• independent analysis
• blank determinations
• variation in sample size
 Types of Error
Random Error (indeterminate error)
It is always present, cannot be corrected, and is
the ultimate limitation on the determination of a
quantity.
Types of Random Errors
- reading a scale on an instrument caused by the
finite thickness of the lines on the scale
- electrical noise
Random error in a buret reading is about ± 0.02 mL
If Initial reading is 45.06 ± 0.02 mL
Final reading is 12.67± 0.02 mL
What is the precision (±) of the delivered volume?
The errors in the IR and FR are absolute uncertainties

The relative uncertainty is 0.02mL/45.06mL *100 =

0.04%
The larger measurement, the smaller the relative
uncertainty
 Can you hit the bull's-eye?

Three shooters
with three arrows
each to shoot.

How do they Both accurate Precise but not Neither accurate

compare? and precise accurate nor precise

Systematic Random
(determinate) (indeterminate)
error error

Can you define accuracy and precision?

 Precision and Accuracy
Precision
Reproducibility

Accuracy (AKA bias)

closeness to accepted value

An ideal procedure provides both precision and accuracy.

Does that mean you can be precisely wrong? WHAT??

 Absolute Uncertainty (Error)
• accuracy
• bias
• systematic error
• same units as measurement

absolute uncertainty = (your value - true value)

= (E.V.– T.V.)
Bias is the offset
between the
population mean
and the true value
of the property
measured.

population true
mean value
bias

 𝛾 𝑥 = 𝜇 𝑥 −   𝜉
 …and NOW

The Real Rule of Significant Figures

The number of figures used to express a
calculated result should be consistent with the
uncertainty in that result.

Or – The answer should have the same number of

decimal places as the ERROR..
 Relative Uncertainty (Error)

  units (ratio of numbers with same units)

• no

relative uncertainty

% relative uncertainty ·100

 Propagation of Error

When possible uncertainty is expressed as a

standard deviation or as a confidence interval -
more on this later!

applies only to random error

WHY???
 Propagation of Error
•  
Addition and Subtraction
uncertainty in addition and subtraction
Example
 28.51
In a titration, the initial reading on the burette is
mL and the final reading is 35.67 mL, both
with an uncertainty of ±0.02 mL. What is the final
volume of titrant used including the error?

Final volume - initial volume = volume delivered

35.67 mL – 28.51 mL = 7.16 ± ? mL

= 0.028…..mL

Applying the real rule of sig. figs.

The final volume (with error) is: 7.16 ± 0.03 mL

 Propagation of Error
Example
 
•Multiplication and Division
 through an electrical circuit is Q = I x t
The quantity of charge, Q in coulombs passing

  e1 2 e2 2

√(
(I is the current in amperes and t is the time
𝑒=x ∙
x1 ) ( )
+
x2
in seconds). When a current of 0.15 ± 0.01 A
passes through the circuit for 120 ± 1 sec,
calculate the total charge (including the
or absolute and percent relative uncertainty.

2 2 2
 % e=√ ( % e1 ) + ( % e2 ) + ( % e3 ) Q= (0.15 A) (120 sec.) = 18 ± ? C

= 1.209……

= 6.7 %

percent relative uncertainty applying the real rule of sig. figs.

%·100
The total charge would be 18 ± 1 C

NOTE: The textbook always calculates the %e for multiplication and division
 Propagation of Error
 
•Exponents and Logarithms
uncertainty for exponents
y = xa %ey = a %ex or
y = 10x
Example
  pH of a solution is defined as pH = -Iog[H+]
The
where, [H+] is the molar concentration of H+. If the pH of a solution is 3.72 ± 0.03 M,
what is the [H+] and its absolute uncertainty?

[H+]=10-pH =10-3.72 = 1.91 x 10-4 M ; = (1.91 x 10-4 M) (2.3026) (0.03)

=1.32 x 10-5 = 0.132 x 10-4

The total [H+] concentration would be 1.9 (± 0.1) x10-4 M

 Propagation of Error
 
•Exponents and Logarithms
uncertainty for logarithms

uncertainty for antilogarithms