Errors

CHEM 315 Darwin F. Reyes, RCh, MSc

Chemistry and Environmental
Analytical Science Dept., CAS, NEUST
Chemistry I
Discussion Outline

• Experimental errors
• Uncertainties

2
 Experimental error

Every measurement has some uncertainty, which is called experimental

error. Conclusions can be expressed with a high or a low degree of confidence,
but never with complete certainty.

• Systematic error, also called determinate error, arises from a flaw in equipment or
the design of an experiment. Systematic error is reproducible when the
experiment is repeated, and this error can be discovered and corrected.
• Random error, also called indeterminate error, arises from the effects of
uncontrolled (and maybe uncontrollable) variables in the measurement. It is
always present and cannot be corrected.

Harris DC (2011). Quantitative Chemical Analysis (8th ed) New York, NY: W.H. Freeman and Company 3
 Experimental error
Systematic error

There are three types of systematic errors:

• Instrumental errors are caused by nonideal instrument behavior, by faulty

calibrations, or by use under inappropriate conditions.
• Method errors arise from nonideal chemical or physical behavior of analytical
systems.
• Personal errors result from the carelessness, inattention, or personal
limitations of the experimenter

Harris DC (2011). Quantitative Chemical Analysis (8th ed) New York, NY: W.H. Freeman and Company 4
 Accuracy and precision

• Precision describes the

reproducibility of a result. If you
measure a quantity several times and
the values agree closely with one
another, your measurement is precise.
If the values vary widely, your
measurement is not precise.

• Accuracy describes how close a

measured value is to the “true” value.

Google images 5
Harris DC (2011). Quantitative Chemical Analysis (8th ed) New York, NY: W.H. Freeman and Company
 Uncertainty
• Absolute uncertainty expresses the margin of uncertainty associated with a
measurement.

• Relative uncertainty compares the size of the absolute uncertainty with the
size of its associated measurement.

Harris DC (2011). Quantitative Chemical Analysis (8th ed) New York, NY: W.H. Freeman and Company 6
 Uncertainty

Google images 7
 Uncertainty
The relative uncertainty of a pipet reading of 12.35 ± 0.02 mL is a dimensionless
quotient:

Harris DC (2011). Quantitative Chemical Analysis (8th ed) New York, NY: W.H. Freeman and Company 8
 Propagation of uncertainty
Addition and Subtraction

For addition and subtraction, the uncertainty in the answer is

obtained from the absolute uncertainties of the individual terms as
follows:

Harris DC (2011). Quantitative Chemical Analysis (8th ed) New York, NY: W.H. Freeman and Company 9
 Propagation of uncertainty
Addition and Subtraction

Harris DC (2011). Quantitative Chemical Analysis (8th ed) New York, NY: W.H. Freeman and Company 10
 Propagation of uncertainty

SOLUTION:

Therefore, the uncertainty in

volume delivered is ±0.03 mL
Harris DC (2011). Quantitative Chemical Analysis (8th ed) New York, NY: W.H. Freeman and Company 11
 Propagation of uncertainty
Multiplication and Division

For multiplication and division, first convert all uncertainties into

percent relative uncertainties. Then calculate the error of the product
or quotient as follows:

Harris DC (2011). Quantitative Chemical Analysis (8th ed) New York, NY: W.H. Freeman and Company 12
 Propagation of uncertainty
Multiplication and Division

Harris DC (2011). Quantitative Chemical Analysis (8th ed) New York, NY: W.H. Freeman and Company 13
 Propagation of uncertainty
Multiplication and Division
• To convert relative uncertainty into absolute uncertainty,

Harris DC (2011). Quantitative Chemical Analysis (8th ed) New York, NY: W.H. Freeman and Company 14