Unit V: Laboratory Safety and Error Analysis

Unit V: Laboratory Safety and Error Analysis (9 hrs)

i. Laboratory Safety
Storage and handling of corrosive, toxic and poisonous chemicals-simple first aid
procedure for acid and alkali in eye, acid and alkali burns, heat burns and cut by glasses.

ii. Error Analysis

Accuracy, precision, classification of errors, minimization of errors, significant figures,
mean and standard deviation – method of least squares – student Q test.

Error Analysis

Uncertainity in common equipment are

Meter balance 0.0001 g

pipette 0.01 mL
burette 0.02 mL etc…

What are Significant Figures?

“The significant figures of numbers are digits convey the meaning that contributes to its
measurement resolution”. The number 13.2 comprises three significant digits. Non-zero digits are
always significant. 3.14159 has 6 significant digits (all the numbers give you useful information).
Thus, 67 has 2 significant digits, and 67.3 has three significant digits.
1000 has 1 significant digit (only the one is interesting; you don’t know anything for sure about the
units, tens and hundreds of places; the zeroes may just be placeholders; Similarly for decimals,
0.00069 has 2 significant digits (only the 6 and 9 tell us something; the other zeroes are
placeholders, only providing information about the relative size). But this rule has an exception, as in
the case of 0.000690 has 3 significant digits (that last zero tells us that the measurement was made
accurate to that last digit, which just happened to have a value of zero). one thousand six (1006) has
4 significant digits (the one and six are significant, and we have to count the zeroes because they’re
between 2 the significant digits).

Application of Significant Figures

These examples can be incorporated into a list of rules for Significant Figures;

 All non-zero digits are significant: 4.321g has four significant figures.
 Zeroes between non-zero digits are significant: 1002 kg has 4 figures.

 Leading zeros to the left of the first non-zero digits are not significant;

 Trailing zeroes that are also to the right of a decimal point in a number are significant:0.0260
mL has three significant figures.
  When a number ends in zeroes that are not to the right of a decimal point, the zeroes are not
necessarily significant: 140 kilometers maybe 2 or 3 significant figures.

To resolve this confusion presented by the last rule, we can use the standard exponential
representation of the numbers. For example,
3.69 × 104 calories (3 significant figures)
3.069 × 104 calories (4 significant figures)

Rounding off the numerical expressions

1. The digits to be rounded off are all removed together, not one at a time.

2. In the figure, following the last figure to be retained is less than 5, then the last digit
retained is not altered.

3. In the figure, following the last figure to be retained is greater than 5, then the last digit
retained is increased by one.

4. In the figure, following the last figure to be retained is 5, and at least one of the other
digits to be removed is non-zero, the last digit retained is increased by one.

5. If the figure following the last figure to be retained is five and all other digits to be
removed are zero, the last digit retained is not altered if it is even but is increased by one
if it is odd.

Problems

Round off the following numbers to 3 significant figures

(a) 75.8437 (Rule 1 & 2) Ans : 75.8

(b) 59.873 (Rule 1 & 3) Ans : 59. 9

(c) 68.752 ( Rule 1 & 4) Ans : 68.8

(d) 47.250 (Rule 1 & 5) Ans : 47.2

(e) 83.35 (Rule 1 & 5) Ans : 83.4

Addition/Subtraction and Multiplication/Division

(a) 42.71 + 9.643 + 8.0 = 60.353

Ans : 60.4 (8.0 has only one figure to the right of the decimal point)

(b) 0.165 x 10.487 = 1.730355

Ans: 1.73 (0.165 has three significant figures)

Precision and Accuracy

Precision refers to the amount of scatter in a set of numbers presumed to measure the same
quantity. For example, suppose you repeatedly placed the same coin on an analytical balance.
The scatter in your results would define the precision of the measurement.
“The degree of agreement between two or more replicate measurements made on a sample ina
n identical manner is known as the precision of the measurement”

Accuracy refers to the degree to which the set of numbers represents the "true" value of the
quantity. If, in the above example, the balance were not properly leveled, it might give good
precision, but the value could be wrong, thereby leading to poor accuracy.
“The closeness of a measurement or a set of measurements to the true or accepted value”

Difference between Precision and Accuracy

Accuracy Precision
Agreement between an experimental result and Agreement between several experimental
true value of a given quantity results obtained for the same quantity under
identical conditions
Can never be determined exactly because true Determined exactly by replicate measurements
value of a quantity is never known (Accepted of the same quantity
value is used)
Expressed in terms of absolute error or relative Expressed in terms of various types of
error deviations from the mean
Accurate items have to be precise in most cases Precise items may or may not be accurate
The error distribution curve for less accurate The error distribution curve for less precise
differs from more accurate set of differs from more precise set of measurements
measurements only with respect to the position with respect to scatter or spread or dispersion
of the mean value
ERRORS -webformulas
Analytical chemistry is based on reliability, reproducibility and accuracy. However, every
measurement has some degree of uncertainty and is limited by the reliability of measuring
instrument and the skill of the person making the measurement. Such uncertainty should be
reported correctly, which is called as error in analytical chemistry.

Error is defined as the numerical difference between a measured value and the absolute value

Absolute Error
Absolute error in measurement refers to the actual amount of error in the measurement. The
absolute error of the measurement shows how large the error actually is. Absolute error is
inadequate due to the fact that it does not give any details regarding the importance or the
graveness of the error. If you are measure distances between cities kilometers apart, an error of a
few centimeters is negligible and is irrelevant. On the other hand, an error of centimeters when
measuring small machine parts is a very significant error. Both the errors are in the order of
centimeters, but the second error is more severe than the first.
Absolute Error can be represented by the expression;

Eabsolute=|xmeasured−xaccepted|
For example, if you know a length is 3.535 m + 0.004 m, then 0.004 m is an absolute error. The
absolute error is the difference between the measured value and the actual value.

Relative Error
Relative error represents the ratio of the absolute error of the measurement to the accepted
measurement. This way we can determine the magnitude of the absolute error in terms of the actual
size of the measurement. If the true measurement of the object is not known then the relative error is
found using the measured value. The expression for relative error is;

Erelative=Eabsolutexaccepted
RelativeError=|measuredvalue−actualvalue|actualvalue

Percentage Error
Errors in measurement may also be expressed in terms of percentage. This is similar to relative
error except that the error here is converted to a percent value. The percentage error is found by
multiplying the relative error by 100%.

percentofError=|measuredvalue−actualvalue|actualvalue∗100 %
This brings us to an end on the article on absolute error, relative error, and tolerance, the major
ways of expressing errors in measurements.

Classification of Errors:
Errors are classified in two types – Systemic (Determinate) and Random (Indeterminate) errors

Systemic (Determinate) errors:

Errors which can be avoided or whose magnitude can be determined is called as systemic errors.
It can be determinable and presumably can be either avoided or corrected. Systemic errors
further classified as

 Operational and personal error

 Instrumental error
 Errors of method
 Additive or proportional error

Operational and personal error:

Errors for which the individual analyst is responsible and are not connected with the method or
procedure is called as personal errors e.g. unable to judge color change

When errors occur during operation is called as operational error e.g. transfers of solution,
effervescence, incomplete drying, underweighting of precipitates, overweighing of precipitates,
and insufficient cooling of precipitates. These errors are physical in nature and occur when sound
analytical techniques is not followed

Instrumental and Reagent errors:

Errors occur due to faulty instrument or reagent containing impurities e.g. un-calibrated weights,
un-calibrated burette, pipette and measuring flasks.

Errors of Method:
When errors occur due to method, it is difficult to correct. In gravimetric analysis, error occurs
due to Insolubility of precipitates, co-precipitates, post-precipitates, decomposition, and
volatilization.

In titrimetric analysis errors occur due to failure of reaction, side reaction, reaction of substance
other than the constituent being determined, difference between observed end point and the
stoichiometric equivalence point of a reaction.

Additive or proportional errors:

Additive error does not depend on constituent present in the determination e.g. loss in weight of
a crucible in which a precipitate is ignited.

Proportional error depends on the amount of the constituent e.g. impurities in standard
compound.

Random Errors:
It occurs accidentally or randomly so called as indeterminate or accidental or random error.
Analyst has no control in this error. It follows a random distribution and a mathematical law of
probability can be applied.

Random and Systematic Errors

The scatter of results which leads to the concept of precision is attributed to random errors
which are presumed to originate from external influences that:
1. are large in number,
2. are unknown and therefore uncontrollable and unpredictable,
Chem 75 Winter, 2016
Error Analysis Page 3
3. cause relatively small individual effects, and
4. act independently.
Defects in accuracy are often caused by systematic errors in a set of data. These refer to a
consistent shift of all values away from the "true" value, such as might be caused by a faulty
measuring device or other undetected external influence which acts in the same direction on all
measurements. For example, suppose the clock used to measure tblue was running consistently
10% slow. Then, all timings made with it will be 10% too small and repetitive measurements
(with the same clock) will not reveal this deficiency.
The distinction between random and systematic error is rarely sharp, and much "random
error" can be attributed to inadequate experimental design. In some experiments it is worth
considerable effort to determine whether the "random error" is indeed random.
Mean and Standard deviation
Method of least squares – student Q test
Minimisation of Errors

Analyst has no control on random errors but systemic errors can be reduced by
following methods.

Calibration of apparatus: By calibrating all the instruments, errors can be

minimized and appropriate corrections are applied to the original measurements.

Control determination: standard substance is used in experiment in identical

experimental condition to minimize the errors.

Blank determination: By omitting sample, a determination is carried out in

identical condition to minimize the errors occurs due to impurities present in
reagent.

Independent method of analysis: It is carried out to maintain accuracy of the

result e. g. Iron (III) is first determined gravimetrically by precipitation method as
iron (III) hydroxide and then determined titrimetrically by reduction to the iron (II)
state.

Parallel determination: Instead of single determination, duplicate or triplicate

determination is carried out to minimize the possibilities of accidental errors.

Standard edition: This method is generally applied to physico-chemical

procedures such as polarography and spectrophotometry.

Internal standards: It is used in spectroscopic and chromatographic

determination.

Amplification methods: It is used when a very small amount of material is to be

measured which is beyond the limit of the apparatus.

Isotopic dilution: It is used for the compound containing radio-active isotope.

electronic instruments and measurement

The static error of a measuring instrument is the numerical difference between the true
value of a quantity and its value as obtained by measurement. This causes the repeated
measurement of the same quantity to give different indications, and thus, precision is an
important characteristic in electronic instruments.
Following are the three main types of static errors:
I. Gross Errors – These errors are mainly due to human mistakes in reading or in using
instruments or errors in recording observations.
 Errors may occur also due to incorrect adjustment of instruments and
computational mistakes.
 One of the basic gross errors that occurs frequently is the improper use of an
instrument.
 Systematic Errors – These errors are due to shortcomings of the instrument,
such as defective or worn parts, ageing, or effects of the environment on the
instrument. There are basically three types of systematic errors, namely –
i. Instrumental – They are inherent in measuring instruments, because of their
mechanical structure (e.g.: irregular spring tensions or stretching of a spring).
ii. Environmental – They are due to conditions external to the measuring device,
including conditions in the area surrounding the instrument, such as the effects of
change in temperature, humidity, barometric pressure, or of magnetic or
electrostatic fields.
iii. Observational – They are introduced by the observer. The most common
error is the parallax error (when the pointer fluctuates between different readings,
and the reading is taken arbitrarily) introduced in reading a meter scale, and the
error of estimation when obtaining a reading from a meter scale.
iv. In general, these are also subdivided into two – static and dynamic.
II. Random Errors – These are the errors that remain after gross and systematic errors
have substantially been reduced or at least accounted for.
 They are generally an accumulation of a large number of small effects and may
be of real concern only in measurements requiring high degree of accuracy.
 They are due to unknown causes, not determinable in the ordinary process of
making measurements.
Methods of minimization –
 Gross errors cannot be completely eliminated, but can be minimized by taking
proper care in reading and recording of the measurement parameter. One
should, therefore, not be completely dependent on a single reading
 Instrumental Systematic errors can be avoided by
a. selecting a suitable instrument for the particular measurement applications
b. applying correction factors after determining the amount of instrumental error
c. calibrating the instrument against a standard
 Environmental Systematic errors can be avoided by air conditioning, hermetically
sealing certain components in the instruments, and using magnetic shields
 Observational Systematic errors can be avoided by concentrating on one
particular measurement process at a time. Clearing out the area where the
instrument is placed will also help the observer focus
 Random errors can be treated mathematically using laws of probability. The idea
is to repeat the measurement to gain high precision.