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ACCURACY AND PRECISION

Accuracy
Accuracy is how close a measured value is to the actual (true) value. Accuracy describes how
close an approximation is to a correct answer. Thus, accuracy is the measure of the difference
Between the experimental value or mean value of a set of measurements and the true value.
Accuracy = Mean value True value
Smaller is the difference between the mean value and the true value more is the accuracy.
For example, suppose your math textbook tells you that the value of pi (n) is 3.14. You do a careful
measurement by drawing a circle and measuring the circumference and diameter, and then you
divide the circumference by the diameter to get a value for pi (1t) of 3.16.
The accuracy of your answer is how much it differs from the accepted value.
In this case, the accuracy is 3.16- 3.14 = 0.02.

Precision
Precision is how close the measured values are to each other. Precision describes how many digits
we use to approximate a particular value. In simple words, it is the difference between the measured
value and the arithmetic mean value for a series of measurements, i.e.,
Precision = Individual value Arithmetic mean value
The idea is illustrated by the following examples:

(i) Target shot by arrows. If you shoot a quiver of arrows at a target, several outcomes are possible.
If all of the arrows that you shoot go straight to the bull s eye, then your aim is both accurate and
precise.
If, however, the arrows cluster in an area immediately to the right of the hulls eye, your aim is
precise, but not accurate.

If your aim is bad and the arrows hit positions scattered all over the target, then your aim is neither
accurate nor precise.
(ii) The value of (pi) is 2217. Suppose the value is written as 3.1417 and 3.1392838. Looking at
the value, the second number has higher precision, but it would appear that the first is more accurate.
(Actual value is 3.142857143.)
(iii) Measurement of a pencil on two different scales. How long is the pencil? The best you can
say looking at the scale I, is about 9 centimeters. You might guess and say about 9.5 centimeters,
but the decimal place is just a guess. Because the smallest unit on the ruler you are using is one
centimeter, the precision of your measurement is to the nearest centimeter.

Now look at the scale-II. Here we are using a different ruler to measure the pencil.
How long is the pencil? The best you can say is about 9.5 centimeters. Again, you might guess and
say about 9.51 centimeters, but the second decimal place is just a guess. Because the smallest unit
on the ruler you are now using is one millimeter (one tenth of a centimeter), the precision of your
measurement is to the nearest millimeter, or tenth of a centimeter.

This second measurement is more precise, because you used a smaller unit to measure with.
UNCERTAINTY IN MEASUREMENT

The study of chemistry involves both theoretical as well as practical aspect which further deals with
qualitative and quantitative measurements. While dealing with calculations the meaningful way is to
handle the numbers conveniently and present the data realistically with certainty to the extent
possible.
SIGNIFICANT FIGURES
Experimental measurements have some uncertainty associated with them. However, one would
always like the results to be precise and accurate. These aspects depend on the accuracy of
measuring device and the skill of the operator.
A convenient method of expressing the uncertainty in measurement is to express it in terms of
significant figures. In this method, it is assumed that all the digits are known with certainty except the
last digit which is uncertain to the extent of 1 in that decimal place. Thus, a measured quantity is
expressed in terms of such a number which includes all digits which are certain and a last digit which
is uncertain. The total number of digits in the number of significant figures.
The number of significant figures in a measurement is the number of figures that are known with
certainty plus one that is uncertain, beginning with the first non-zero digit.
In order to determine the significant figures in a measured quantity the following rules should be
applied.
1. All non-zero digits are significant.
For example, 165 cm has three significant figures; 0.165 has also three significant figures. Similarly,
2006 has four significant figures, 9.05 has three significant figures, etc.
2. Zeros to the left of the first non-zero digit in the number are not significant.
For example, 0.005 g has only one significant figure, 0.026 g has two significant figures.
3. Zeros between non-zero digits are significant.
For example, 2.05 g has three significant figures.
4. Zeros to the right of the decimal point are significant.
For example, 5.00 g, 0.050 g, 0.5000 g have three, two and four significant figures respectively.
5. If a number ends in zeros that are not to the right of a decimal, the zeros may or may not be
significant.
For example, 1500 g may have two, three or four significant figures.
The ambiguity in the last point can be removed by expressing the number in scientific notation.

In scientific notation the number is written in the standard exponential form as N x 10 n.


N = a number with a single non-zero digit to the left of the decimal point.
n = some integer.
For example, a mass of 1500 g can be expressed in scientific notation in the following forms
depending upon whether it has two, three or four significant figures
1.5 x 103 g

(Two significant figures)

1.50 x 103 g (Three significant figures)


1.500 x 103 g (Four significant figures)
In these expressions all the zeros to the right of the decimal point are significant. The exponential
notation is an excellent way of expressing significant figures in very large or very small
measurements. For example, Avogadros constant is expressed as 6.022 x 1023 mol-1 and Plancks
constant as 6.62 x w-34 Js.
Lastly, it may be emphasized that exact integral numbers, such as number of pencils in a dozen
pencils or number of grams in a kilogram do not have any uncertainty associated with them and as
such these numbers have an infinite number of significant figures.

CALCULATIONS WITH SIGNIFICANT FIGURES


During quantitative studies, the scientists have to do calculations with numbers used for various
measured physical quantities. These numbers generally, have different number of significant digits
depending upon the accuracy with which a particular measurement is made. While carrying out
calculations with these numbers, the rule used is that the accuracy of the final result is limited to the
least accurate measurement. In other words, final result cannot be more accurate than the least
accurate number involved in the calculation.
In order to understand this let us suppose that in a simple experiment two samples A and B are
weighed by balances of different accuracy. Let the weight of sample A be 2.3 g and that of sample B
be 14 g. The first weighing has 2 as the certain digit and 3 as the doubtful digit. The second weighing
has 1 as the certain digit and 4 as the doubtful digit. If the samples A and B are mixed, the final weight
would be expressed as 2.3 + 14 = 16 and not as 16.3. In 16.3 the digit at
unit place is certain whereas it is not so in case of weight of sample B. Thus, if the result is expressed
as 16.3, the final result would be more accurate than the one of the measurements involved in the
calculation, which is not possible.

SOLVED EXAMPLES
1 Example 2.1 . Express the following numbers to four significant figures
(i) 5.607892
(iii) 1.78986 X 103

(ii) 32.392800
(iv) 0.007837.

Solution. (i) As the fifth digit 8 is greater than 5, therefore the result will be expressed as 5.608.
(ii) It will be expressed as 32.39. The digit 2 is dropped and since it is less than 5 the figure is not
rounded off to next number.
(iii) The fifth digit being greater than 5, therefore the result is expressed as 1.790.
(iv) The four digits to be retained are 7, 8, 3 and 7 therefore the number is expressed as 7.837 x 10 -3.
The exponential term does not add to significant figures.
Example 2.2 Express the following numbers to three significant figures:
(1) 6.022 x 5.359

(ii) 5.359

(iii) 0.04597

(iv) 34.216.

Solution. (i) The last digit to be retained is 2 and the digit to be dropped is 2 which is less than 5. The
result will be expressed as 6.02 x1023.
(ii) In this case the last digit to be retained is 5 and the digit to be dropped is 9, which is greater than
5. Hence, the last digit to be retained is increased by one. The number will be written as 5.36.
(iii) The three digits to be retained in this case are 4, 5 and 9. The digit 7 is to be dropped which is
greater than 5. Hence, the last digit to be retained will therefore be increased by one. The number will
be rounded off to three significant digits as 0.0460.
(iv) In this case the digits 1 and 6 will be dropped. Since, the digit following the last digit to be retained
is 1, the last digit will be kept unchanged and the number is written.