Experimental

Error
Lecture 1

Presented by:
Marck Jason B. Tagapan
Experimental Error

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 Experimental Error
Calculate the density of the mineral:

❑ mass (4.635±0.002 g)
❑ volume (1.13±0.05 mL)
mass
ρ= volume

4.635 g
= 1.13 mL

= 4.1018 g/mL 3
 Significant Figures
❑ Significant figures: The number of significant digits in
a number is the minimum required to write the number
in scientific notation.

Example:

➢ 142.7 1.427 x 102 4 significant figures

➢ 1.4270 x 102 5 significant figures
➢ 92 500 9.25 x 102 3 significant figures
9.250 x 102 4 significant figures
9.2500 x 102 5 significant figures
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 Significant Figures
❑ Significant zeros below are bold:

106 0.0106 0.106 0.1060

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Significant Figures

Figure 1. Analog scale of Bausch and Lomb Spectronic 20

spectrophotometer. Percent transmittance is a linear
scale and absorbance is a logarithmic scale.

Absorbance: 0.234
Percent Transmittance: 58.3 6
Significant Figures in Arithmetic

❑ Rounding should only be done on the final answer

(not intermediate results), to avoid accumulating
round-off errors.

❑ Addition and Subtraction

➢If the numbers to be added or subtracted have equal
numbers of digits, the answer goes to the same decimal
place as in any of the individual numbers:

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Significant Figures in Arithmetic

❑ Addition and Subtraction

➢If the numbers being added do not have the
same number of significant figures, we are
limited by the least certain one.

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Significant Figures in Arithmetic

❑ Rules for rounding off numbers

➢ When rounding off, look at all the digits

beyond the last place desired.
➢ If the insignificant figures were less than
halfway, we would round down.
➢ If the insignificant figures were more than
halfway, we would round up.
➢ When the number is exactly halfway, round to
the nearest even digit.
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Significant Figures in Arithmetic

❑ Rules for rounding off numbers

The number 121.794 806 4 should be rounded to

121.795 as the final answer.
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Significant Figures in Arithmetic

❑ Rules for rounding off numbers

43.55 is rounded to 43.6

1.425 x 10-9 is rounded to 1.42 x 10-9
(3 significant figures)
1.42501 x 10-9 is rounded to 1.43 x 10-9

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Significant Figures in Arithmetic

❑ Addition and subtraction:

Express all numbers with the same exponent
and align all numbers with respect to the
decimal point. Round off the answer
according to the number of decimal places in
the number with the fewest decimal places.

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Significant Figures in Arithmetic

❑ Multiplication and division:

Answer is limited to number of digits in the
number with the fewest significant figures.

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Significant Figures in Arithmetic

❑ Logarithms and Antilogarithms:

Number of digits in mantissa of log x 5

number of significant figures in x:

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Significant Figures in Arithmetic

❑ Logarithms and Antilogarithms:

Number of digits in antilog x (= 10x ) =

number of significant figures in mantissa of x:

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Types of Error

❑ Systematic error, also called determinate

error, arises from a flaw in equipment or
the design of an experiment. If you
conduct the experiment again in exactly
the same manner, the error is reproducible.
❑ In principle, systematic error can be
discovered and corrected, although this
may not be easy.

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Types of Error

FIGURE 2. Calibration curve for a 50-mL buret. The volume delivered can be
read to the nearest 0.1 mL. If your buret reading is 29.43 mL, you can
find the correction factor accurately enough by locating 29.4 mL on
the graph. The correction factor on the ordinate (y-axis) for 29.4 mL
on the abscissa (x-axis) is 20.03 mL (to the nearest 0.01 mL). 17
Case Study in Ethics
Systematic Error in Ozone Measurement

Schematic of 2B Technologies personal ozone monitor. The solenoid alternately admits ambient
air or air that has been scrubbed free of O3. Absorbance of ultraviolet radiation from the Hg
lamp is proportional to O3 concentration. [Information from P. C. Andersen, C. J. Williford, and J.
W. Birks, “Miniature Personal Ozone Monitor Based on UV Absorbance,” Anal. Chem. 2010, 82,
7924.] 18
Certified Reference Materials

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Ways to detect systematic error

➢ Analyze a known sample, such as a certified

reference material. Your method should reproduce
the known answer.

➢ Analyze blank samples containing no analyte being

sought. If you observe a nonzero result, your
method responds to more than you intend.

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Ways to detect systematic error

➢ Use different analytical methods to measure the

same quantity. If results do not agree, there is error
in one (or more) of the methods.

➢ Round robin experiment: Different people in several

laboratories analyze identical samples by the same
or different methods. Disagreement beyond the
estimated random error is systematic error.

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 Systematic Error
Rainwater pH Measurement: Effect of Junction Potential

(a) pH of precipitation in the U.S. in 2011. The lower the pH, the more acidic the water.
[Data from National Atmospheric Deposition Program (NRSP-3). (2007). NADP Program
Office, Illinois State Water Survey, 2204 Griffith Dr., Champaign, IL 61820,
http://nadp.sws.uiuc.edu.]
(b) (b) pH of rain in Europe. No values are reported for Italy and Greece. [Data from H.
Rodhe, F. Dentener, and M. Schulz, Environ. Sci. Technol. 2002, 36, 4382.]
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 Systematic Error
Rainwater pH Measurement: Effect of Junction Potential

Figure A. pH of rainwater from identical Figure B. Rainwater pH measured by using

samples measured at 17 different low ionic strength HCl for
labs using standard buffers for calibration.
calibration. Letters designate
different types of pH electrodes.
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Types of Error

❑ random error, also called indeterminate

error, arises from uncontrolled (and maybe
uncontrollable) variables in the
measurement.
❑ it might be reduced by a better
experiment.
❑ there is random error associated with
reading a scale.

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Precision and Accuracy

❑ Precision: reproducibility
❑ Accuracy: nearness to the “truth”

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 Random and Systematic Errors

Table 1. Data demonstrating random and systematic errors

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Random and Systematic Errors

Figure 1. Bias and precision:

dot-plots of the data in
Table 1.
a. precise but biased
b. imprecise but unbiased
c. imprecise but biased
d. precise and unbiased

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 Random and Systematic Errors

Table 2. Random and systematic errors

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Random and Systematic Errors

❑precision describes random error

❑bias describes systematic error

❑accuracy incorporates both types of error

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Random and Systematic Errors

❑precision describes random error

❑bias describes systematic error

❑accuracy incorporates both types of error

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Uncertainty in a Buret Reading

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Multiplication and Division

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Mixed Operations

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The Real Rule for Significant Figures

❑The real rule: The first uncertain figure is the last significant figure.

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Propagation of Uncertainty

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Propagation of Uncertainty from Systematic Error

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 Uncertainty in Molecular Mass

❑Propagation of systematic uncertainty: Uncertainty in mass of n

identical atoms = n x (uncertainty in atomic mass)

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Multiple Deliveries from One Pipet: The Virtue of Calibration

❑A 25-mL Class A volumetric pipet is certified by the manufacturer

to deliver 25.00 ± 0.03 mL. If you use an uncalibrated 25-mL
Class A volumetric pipet four times to deliver a total of 100 mL,
what is the uncertainty in 100 mL?

❑The difference between 25.00 mL and the actual volume

delivered by a particular pipet is a systematic error.

❑Calibration eliminates systematic error, because we would know

that the pipet always delivers, say, 24.991 ± 0.006 mL. The
uncertainty ± 0.006 mL is a random error.

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Multiple Deliveries from One Pipet: The Virtue of Calibration

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