MEASUREMENTS AND ERRORS

LEARNING OBJECTIVES
1. Evaluate the accuracy of the measurement in terms of absolute error and relative error.
2. Evaluate the accuracy of the measurements, relating it to the dispersion of the values by means of
the calculation of the standard deviation.
3. Examine the basic criteria for reporting experimental results with a certain
number of digits and express any result from a mathematical operation, with
the number of significant figures corresponding.
4. Apply criteria of accuracy and precision for the selection of a measuring instrument.
5. Calibrate the pipettes and the graduated cylinders.

REAGENTS
. Sulfochromic mixture or Alcoholic Potash
. Distilled water

MATERIALS
. Scale
. 25 ml graduated cylinder . 25 ml volumetric pipette
. Graduated Pipette of 10 ml . 125 ml Erlenmeyer
. Thermometer . 15 ml volumetric pipette
. Propipette

POINTS OF INTEREST
. Preparation of laboratory material
Common types of errors in laboratories
. Determined Errors
. Indeterminate Errors
. Calculation of error and percent error
Statistical treatment of finite samples
Concept of:
. Accuracy and Precision (Absolute Error and Standard Deviation)
Use of significant figures
Calibration of volumetric instruments
Density

THEORETICAL INTRODUCTION
As Chemistry has evolved, chemists have developed instruments and techniques
for basic operations in the laboratory. This practice explains some in detail.
Commonly used materials for handling reagents in a chemistry laboratory can
classify as follows:
 MEASUREMENTS AND ERRORS
Material that Allows the Handling of Liquids and Solutions

High Precision and Accuracy Material Low Precision and Accuracy Material Non-Quantitative Uses

Graduated Pipettes Graduated Cylinder Bottles to Contain Reagents

Volumetric Pipettes Piceta or Washer Bottle
Burettes Beakers
Calibrated Balls Erlenmeyer or Flask

High Precision and Accuracy Material

It is the material that allows us to take volume measurements that require aprecision and
accuracyhigh, such as, take a aliquot, dilute to a certain volume, determine the point
Finally, in an assessment, relate the operation to each of the instruments mentioned in the.
diagram.

Low Precision and Accuracy Material

It is the material that allows us to take volume measurements when a large one is not necessary.
accuracy or precision of the measurement, such as qualitative analyses, minimum volumes to dissolve a
solid, etc.

Non-Quantitative Uses
Non-quantitative uses include those materials that allow us to store reagents or
samples, performing evaporations, digestion of precipitates, heating liquids, etc.
For more details regarding the uses and handling of the material mentioned above, see in Material of
Laboratory.

UNCERTAINTY IN MEASUREMENTS
In most experimental procedures, a great effort is made to gather the
data and most of these have become quantitative data; this means that they
they derive from the measurements. When any measurement is made, it is necessary to consider that there exists a
uncertainty and it is important to develop skills to determine, analyze the data and draw conclusions
conclusions that are truly justified.
Most of the techniques we consider for this data evaluation are based on
statistical concepts. It is increasingly recognized that statistical methods are effective in
planning of the experiments that will provide the most information from the minimum number of
measurements, and to 'abbreviate' the data in such a way that its meaning is presented concisely.
On the other hand, and as a very important point, it should not be expected that the statistics will decrease the
the need to obtain good measurements, taking into account that statistical methods are more
efficient when applied to valid data.

ERRORS
The term error is used to refer to the numerical difference between the measured value and the value
accepted as real. The real value of any amount is actually a philosophical abstraction, something
that man is not destined to know, although scientists feel that it exists and think that
 MEASUREMENTS AND ERRORS
they can access it, more and more closely, when their measurements become more
refined.

Determined errors
Errors that can be attributed to defined causes are called determined errors or
systematic. Their causes may be: a) the analysis method that reflects the properties of the
chemical systems involved, b) the operator's incompetence c) limitations or deterioration of the
measuring devices that do not allow it to operate according to the required standards.
Examples of systematic errors are: the analyst has an inadequate technique in the use of the
scale, the glass material is not properly conditioned, etc.
Within the determined errors, there is another type, instrumental error, which is very easy to
determine in analog measuring instruments, this error is estimated as follows,
A
E
2

Where A is the appreciation of the instrument and can be determined from the difference of the
readings of two values marked on the instrument and the number of divisions that exist between them
according to:

Major Reading Minor Reading

A
N of Divisions

In some volumetric equipment used in chemistry, such as volumetric pipettes, the error
The reading commitment is specified by the manufacturer; which fluctuates between 0.5% of the volume.
read, in precision equipment and 10% in less precise equipment.
For digital devices, the instrumental error is taken as the error in the last digit that appears in the
screen. For example, if the screen shows 12.04, the instrumental error will be 0.01 and it must
report: 12.04 0.01

Indeterminate errors
The errors classified as indeterminate are those that occur despite being very
careful and meticulous. They are fortuitous errors that cannot be further reduced.

ACCURACY AND PRECISION

The terms accuracy and precision that in ordinary conversation are often used as
synonyms must be distinguished carefully in relation to scientific data as they do not mean
the same. An exact result is one that closely matches the real value of a quantity
measure. The comparison is often made based on an inverse measure of accuracy,
What is the error (the smaller the error, the greater the accuracy). The absolute error is the
difference between the experimental value and the real value. It can be in excess (+) or in deficit (-). For
For example, if an analyst finds 20.44% iron in a sample that actually contains 20.34%.
the absolute error (Ea) is

Ea20.44% - 20.34% = 0.10%

 MEASUREMENTS AND ERRORS
The term precision refers to the agreement among a group of results.
experimental; it has no relation to the real value. Precise values may be inaccurate, already
that an error causing deviation from the actual value can affect all measurements equally and
consequently not harm its accuracy. Accuracy is generally expressed in terms of the
deviation. As in the case of the error (mentioned earlier), precision can be expressed in
absolute or relative form. And it is expressed in modulus.

STATISTICAL TREATMENT OF FINITE SAMPLES

The results or data scattered in a random manner are best analyzed through techniques.
statistics.

Measures of central tendency

The central tendency of a group of data is simply the value around which the results
individuals tend to "group together". The mean, x, is a measure of central tendency and its calculation
it simply involves obtaining the average of the individual results:
n
i 1IX
x
n
In general, the mean is the most useful measure of central tendency. There is also the median.
that in an odd number of data points, the middle data point is the one that corresponds to the mode, which is the data that occurs most frequently

It repeats. Speaking in general terms, the median and the mode are measures of central tendency.
much less efficient than average.

Measures of variability
For a finite number of values, the simplest measure of variability is the range, which is the
difference between the largest and the smallest value. Like the median, the range is useful in some
sometimes in the statistical treatment of small samples, but speaking generally, it is a
ineffective measure of variability. Note, for example, that an 'anomalous' result exerts a
strong impact on the range.
In statistics, the standard deviation is much more significant than the range. For a finite number.
the symbol s is used to denote the standard deviation. The standard deviation is
calculate using the following formula.

N
 x i x 2
i 1
S
N 1

xiEach of the values

observed
x Media
N = Number of determinations
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If N is large (let's say 30 or more), then, of course, it is imperceptible that the term in
the denominator be N-1 (which is strictly correct) or N, remember this premise at the time
to perform the direct calculation with the calculator since most have both forms of it
calculation.

SIGNIFICANT FIGURES AND RULES FOR CALCULATION

Most scientists define significant figures as follows: they are said to be figures
significant all the numbers that are safe. It is important to use only significant figures when
to express data and analytical results in order to correctly report the error with which it
measures are taken or results are obtained. The use of many or very few figures
significant can confuse another person regarding the accuracy (repeatability of a series of
data) from the analytical data.
When reporting a result, it is important to take into account the number of significant figures that
it has the measure of variability. For example, if an average of the measures taken of a
digital scale with a precision of 0.01 grams, was 2.6545678 and the standard deviation was
0.0563456 should be rounded and reported: 2.65 0.06
Similarly, if you need to weigh 2.65 g of a Sodium Chloride sample on a balance with a
sensitivity of 0.01 g, should be reported: 2.65 ±0.01 g

CALIBRATION OF VOLUMETRIC INSTRUMENTS

Determination of the true volume measured by the instrument, through the mass of the liquid
associated with the volume read. It must take into account the density of the liquid.

CONDITIONING OF LABORATORY MATERIAL

Cleaning of Glass Material

The perfect cleaning of the glass material that will be used in the laboratories is of great importance.
importance. Before using any laboratory material, make sure it is clean.
Generally, this material is cleaned with a solution of a good detergent followed by rinsing.
with tap water and then with distilled water. In order to facilitate the cleaning of these equipment,
Generally, laboratories are equipped with brushes of different sizes, suitable for the...
requirements of the same. If there are drops adhered to the walls of the material, it is an indication that
it is not completely clean, so the use of sulfochromic mixture or potash is recommended
alcohol followed by a rinse with tap water and finally distilled water.
When the experiment requires it, it is advisable to dry the material, but without contaminating it. To such
it is recommended to let it drain well, or to dry it in the stove or by using air
fat-free compressed

Cured from the Pipette

The "curing" of a glass material is done whenever one wants to ensure that it does not change.
concentration of the solution within that material, with the 'curing' it aims to 'replace' the rest of
distilled water for the solution to be used.
 MEASUREMENTS AND ERRORS
For the case of the pipette, it is inserted (deep enough) through its lower end,
finished in a point, in the container that holds the liquid to be measured.1Then it is inhaled
slowly with the pro pipette, in such a way as to introduce enough liquid to fill the bulb
approximately up to a third of its capacity. Holding it almost horizontal, the pipette is turned
carefully until the liquid covers the entire interior surface, then the liquid is allowed to exit and
the operation is repeated 2 or 3 more times.

OPERATIONS THAT CAN BE CARRIED OUT WITH LABORATORY MATERIAL

Transfer of Liquids from Bottles

When transferring liquids from a bottle containing a reagent, the cap of the bottle must be
holding in the hand, the label of the bottle should be covered by the palm of the hand, so that
so that there is no opportunity to damage it if the liquid spills outside the bottle. When
Pour some reagent, do it slowly to avoid dangerous splashes. To this effect, it is
It is convenient to direct the flow with a clean glass rod towards the inside of the container.

Measure of a Fraction
The liquid is aspirated using a pipette until the volume is 1 or 2 centimeters per.
above the leveling (measurement) mark of the VOLUMETRIC PIPETTE. Care must be taken not to
suck very hard as the liquid can reach the tip of the pipette. The tip is dried with the
help from a filter paper while keeping the lower end resting against the wall of the container that
it contains the starting solution, the liquid meniscus is allowed to drop until it reaches the signal of
fill the volume. After achieving the fill in the pipette, proceed to empty the solution.
contained in it to the container, keeping the lower end of the pipette resting against the wall
this facilitates the drainage of the solution. This operation facilitates the drainage of the solution
contained in the pipette into the container.
Depending on the purpose for which the aliquot is taken, the container may be a calibrated flask.
(dilution of solutions) or an Erlenmeyer (titration).

EXPERIMENTAL WORK
EXPERIMENT NO. 1
Determine the accuracy and the error of the following instruments:
Graduated cylinder 25 ml
10 ml graduated pipette
Thermometer

EXPERIMENT NO. 2
. Take a 25 ml graduated cylinder and measure 25 ml of distilled water.
. Pour the liquid into a conditioned bottle and determine the mass of the water. CONSULT WITH
YOUR TEACHER ABOUT THE BALANCE.
. Determine the measured volume of water by the cylinder using the formula:
D m m
V
V D
1
Remember that the pipette should never be inserted into the reagent bottle to avoid possible contamination.
 MEASUREMENTS AND ERRORS

D= density of water at laboratory temperature.

m= water mass contained in the vial
V = volume of water measured by the cylinder

. Conduct the experiment three times.

EXPERIMENT NO. 3
Take a 25 mL volumetric pipette, previously conditioned, and measure 25 mL of water.
distilled. Determine, just like in the previous experiment, the volume measured by the pipette at
through the weight of the water contained in it. Conduct the experiment in triplicate.

EXPERIMENT No. 4
Take a 15 ml volumetric pipette, previously conditioned, and measure 15 mL of distilled water.
Determine, just like in the previous experiment, the volume measured by the pipette through the
weight of the water contained in it. Conduct the experiment in triplicate.

For each of the experiments, 2, 3, and 4 determine:

. The precision of the measurement expressed in terms of absolute and relative deviation.
. The accuracy of the instrument based on the error and percentage of error. (Take as value
accepted 'real' the volume reported by the manufacturer, both for the graduated cylinder and for the
volumetric pipette the value will be 25.0 mL.

BIBLIOGRAPHY
Skoog, West and Hollard: (1994) Analytical Chemistry. Ed. Mc. Graw Hill.
Quantitative Chemical Analysis
González A., (1988) Measurements and errors in the laboratory. [online]. Available:
The provided text is a URL and cannot be [Link] 2001