Q1. Give source wise classification of determinate error.

Explain and
illustrate each class?
Errors are classified into two types:
Determinate errors (or systematic errors)
Indeterminate errors (or random errors)

DETERMINATE ERRORS
Those types of errors for which atleast in principle a definite cause of source
can be observed are known as determinate type of error. With proper
precaution, elimination of these type of error is possible. Determinate error
are generally unidirectional. They can be of considerable magnitude. As a
result these error can affect the measurement being made. Determinate error
are reproducible and to a certain extent in some cases, predictable as well.
Types of determinate errors: Instrumental errors: use of a measuring device or an instrument
forms an integral part of the measurement. The instrumental error may
arise due to the instrument itself or due to the effect of the
environmental factors on the instrument
Uncertainty in the last digit of a measurement: due to the least count
of the instrument. Least count of an instrument is defined as the
minimum value that it can measure each measuring device possesses a
least count. Least count of an instrument introduces an uncertainty in
the last digit of the measured value. This uncertainty is inherent and
cannot be avoided.
Poorly calibrated glassware and instruments.
Improper response: every instrument is made to work under optimum
conditions. For proper response of the instrument it is necessary.
When optimum conditions are not maintained, the response may not

be proper. It is assumed that under optimum conditions, the instrument

behaves ideally. With improper and non-ideal conditions, the
possibility of errors creeping in cannot be ruled out.

Methodic errors: Methodic errors are errors associated with a

particular method. They are part and parcel of the method and hence
cannot be eliminated but can be minimized. E.g

Solubility of a salt: when a salt gets precipitated, the solution of the

salt. Thus in gravimetric analysis when a metal ion is precipitated as a
sparingly soluble salt its complete removal from the solution is not
possible. This will lead to error.
Addition of excess amount of the titrant: the volumetric analysis the
end point and the equivalence point differ. The difference is known as
titration error. The titration error will be the error associated with the
titration method. The error will get eliminated if the end point and the
equivalence point coincide. This will not be possible in each and
every case. Hence attempt are made to minimise the titration error.
Incomplete decomposition: it is an e.g. of an incomplete reaction.
Many times the precipitate is obtained as one salt and weighed as
some other salt. This involves conversion of one salt to another.
Co-precipitation and post precipitation: in gravimetric analysis these
are common errors. Post precipitation of one salt on the surface of the
other. Whereas in co- precipitation another salt gets incorporated in
the precipitate that is getting formed.
Operational errors: Operational errors are the errors which are due
to the analyst and not because of methods or procedures. The
operational errors are mostly physical in nature and occurs when

sound analytical technique is not followed. Hence these type of errors

can be definitely eliminated. E.g. weighing of the crucible before
cooling, loss of precipitate during filtration, blowing the last drop in
the nozzle of the pipette, improve recording of a measurement, under
washing or over washing of precipitates.
Personal errors: this error arises due to the physical limitations of the
analyst. Colour blindness is an example of physical limitation of the
analyst.
Magnitude wise classification of determinate errors:Magnitude wise determinate errors are classified as constant and
proportionate errors
Constant errors and additive errors
The constant errors are those in which absolute error is independent of
sample size however relative error increase as the sample size is
decreased.
Proportionate errors
The proportionate errors are those in which absolute error increases in
direct proportion to the sample size however relative error remain
constant. Thus in proportionate error relative error remains constant
irrespective of numerical values measured.

OR

Q2) explain the difference between absolute error and relative

error/constant and proportionate error?
Absolute error
The difference between the true value
and the measured value with regards
to the sign is the absolute error.
E= xi- xt

Relative error
the absolute or mean expressed as a
percentage of the true value is the
relative error.
R.E= Absolute error/ true value

Where xi -> measured value

Xt-> true value
Titration error in titrimetric analysis

i.e. R.E= xi-xt/ xt

Constant error
The absolute value of constant error
is independent of sample size.
Absolute error remains same but
relative error increases as the sample
size is decreased.

Proportionate error
The absolute value of a proportionate
error is dependent of sample size
The relative error remains constant
but absolute error increases as the
sample size is increased

Presence of impurities in gravimetric

analysis.

Absolute error

Relative error

The absolute error is the magnitude of the

differences between exact value and
approximation.

The relative error is the absolute error

divided by the magnitude of exact value.

Absolute values have the same units as the

quantities measured.

Relative values are ratios, and have no units.

The ratios are commonly expressed as
fractions

Absolute error can defined when the true

value is zero.

Relative error is undefined when the true

value is zero.

Absolute Accuracy Error

Relative Accuracy Error

Example: 25.13 mL - 25.00 mL = +0.13 mL Example: (( 25.13 mL - 25.00 mL)/25.00

absolute error.
mL) x 100% = 0.52% relative error.
Example: For professional gravimetric
chloride results we must have less than 0.2%

relative error.

Explain the meaning of significance number:

The term significant figures refers to the number of important single digits
(0 through 9 inclusive) in the coefficient of an expression in scientific
notation . The number of significant figures in an expression indicates the
confidence or precision with which an engineer or scientist states a quantity.

Significant figures are arrived at by rounding off an expression after a

calculation is executed. . In any calculation, the number of significant figures
in the solution must be equal to, or less than, the number of significant
figures in the least precise expression or element.
The significant figures of a number are those digits that carry meaning
contributing to its precision.
Decimal expressionScientific notation Sig. figs.
1,222,000.00

0.00003450000

-9,876,543,210

1.222 x 10 6

1.22200000 x 10 6

3.45 x 10 -5

3.450000 x 10 -5

-9.87654 x 10 9

-9.876543210 x 10 9 10
-0.0000000100

-1 x 10 -8

-1.00 x 10 -8

Example : Consider the following product:

2.56 x 10 67 x -8.33 x 10 -54To obtain the product of these two numbers, the
coefficients are multiplied, and the powers of 10 are added. This produces
the following result:
2.56 x (-8.33) x 10 67+(-54)
= 2.56 x (-8.33) x 1067-54 = -21.3248 x 10 13The proper form of common
scientific notation requires that the absolute value of the coefficient be larger
than 1 and less than 10. Thus, the coefficient in the above expression should
be divided by 10 and the power of 10 increased by one, giving:

-2.13248 x 10 14 because both multiplicands in the original product are

specified to only three significant figures, a scientist or engineer will round
off the final expression to three significant figures as well, yielding:
-2.13 x 10 14 as the product

Identifying significant figures:

Specifically, the rules for identifying significant figures when writing or
interpreting numbers are as follows:
All non-zero digits are considered significant. For example, 91 has two
significant figures (9 and 1), while 123.45 has five significant figures (1,
2, 3, 4 and 5).
Zeros appearing anywhere between two non-zero digits are significant.
Example: 101.1203 has seven significant figures: 1, 0, 1, 1, 2, 0 and 3.
Leading zeros are not significant. For example, 0.00052 has two
significant figures: 5 and 2.
Trailing zeros in a number containing a decimal point are significant. For
example, 12.2300 has six significant figures: 1, 2, 2, 3, 0 and 0. The
number 0.000122300 still has only six significant figures (the zeros
before the 1 are not significant). In addition, 120.00 has five significant
figures since it has three trailing zeros. This convention clarifies the
precision of such numbers; for example, if a measurement precise to four
decimal places (0.0001) is given as 12.23 then it might be understood
that only two decimal places of precision are available. Stating the result
as 12.2300 makes clear that it is precise to four decimal places (in this
case, six significant figures).
The significance of trailing zeros in a number not containing a decimal
point can be ambiguous. For example, it may not always be clear if a
number like 1300 is precise to the nearest unit (and just happens
coincidentally to be an exact multiple of a hundred) or if it is only shown
to the nearest hundred due to rounding or uncertainty. Various

conventions exist to address this issue:

A bar may be placed over the last significant figure; any trailing zeros
following this are insignificant. For example, 1300 has three significant
figures (and hence indicates that the number is precise to the nearest ten).
The last significant figure of a number may be underlined; for example,
"2000" has two significant figures.
A decimal point may be placed after the number; for example "100."
indicates specifically that three significant figures are meant.

To round to n significant figures:

If the first non-significant figure is a 5 followed by other non-zero digits,
round up the last significant figure (away from zero). For example, 1.2459 as
the result of a calculation or measurement that only allows for 3 significant
figures should be written 1.25.
If the first non-significant figure is a 5 not followed by any other digits or
followed only by zeros, rounding requires a tie-breaking rule. For example, to
round 1.25 to 2 significant figures:
Round half up (also known as "5/4") rounds up to 1.3. This is the default
rounding method implied in many disciplines if not specified.
Round half to even, which rounds to the nearest even number, rounds down
to 1.2 in this case. The same strategy applied to 1.35 would instead round up
to 1.4.
Replace non-significant figures in front of the decimal by zeros.

Relationship to accuracy and precision in measurement:

Q.3 SIGNIFICANT FIGURES:

All measurements are approximationsno measuring device can give
perfect measurements without experimental uncertainty. By convention, a
mass measured to 13.2 g is said to have an absolute uncertainty of plus or
minus 0.1 g and is said to have been measured to the nearest 0.1 g. In other
words, we are somewhat uncertain about that last digitit could be a "2";

then again, it could be a "1" or a "3". A mass of 13.20 g indicates an absolute

uncertainty of plus or minus 0.01 g.

WHAT IS A "SIGNIFICANT FIGURE"?

The number of significant figures in a result is simply the number of figures
that are known with some degree of reliability. The number 13.2 is said to
have 3 significant figures. The number 13.20 is said to have 4 significant
figures.

RULES FOR DECIDING THE NUMBER OF SIGNIFICANT

FIGURES IN A MEASURED QUANTITY:
(1) All nonzero digits are significant:
1.234 g has 4 significant figures,
1.2 g has 2 significant figures.
(2) Zeroes between nonzero digits are significant:
1002 kg has 4 significant figures,
3.07 mL has 3 significant figures.
(3) Leading zeros to the left of the first nonzero digits are not significant;
such zeroes merely indicate the position of the decimal point:
0.001 oC has only 1 significant figure,
0.012 g has 2 significant figures.
(4) Trailing zeroes that are also to the right of a decimal point in a number
are significant:
0.0230 mL has 3 significant figures,
0.20 g has 2 significant figures.
(5) When a number ends in zeroes that are not to the right of a decimal point,
the zeroes are not necessarily significant:
190 miles may be 2 or 3 significant figures,
50,600 calories may be 3, 4, or 5 significant figures.
The potential ambiguity in the last rule can be avoided by the use of standard

exponential, or "scientific," notation. For example, depending on whether

the number of significant figures is 3, 4, or 5, we would write 50,600
calories as:
5.06 104 calories (3 significant figures)
5.060 104 calories (4 significant figures), or
5.0600 104 calories (5 significant figures).
By writing a number in scientific notation, the number of significant figures
is clearly indicated by the number of numerical figures in the 'digit' term as
shown by these examples. This approach is a reasonable convention to
follow.

WHAT IS AN "EXACT NUMBER"?

Some numbers are exact because they are known with complete
certainty.Most exact numbers are integers: exactly 12 inches are in a foot,
there might be exactly 23 students in a class. Exact numbers are often found
as conversion factors or as counts of objects.
Exact numbers can be considered to have an infinite number of significant
figures. Thus, the number of apparent significant figures in any exact
number can be ignored as a limiting factor in determining the number of
significant figures in the result of a calculation.

RULES FOR MATHEMATICAL OPERATIONS:

In carrying out calculations, the general rule is that the accuracy of a
calculated result is limited by the least accurate measurement involved in the
calculation.
(1) In addition and subtraction, the result is rounded off to the last common
digit occurring furthest to the right in all components. Another way to state
this rule is as follows: in addition and subtraction, the result is rounded off
so that it has the same number of digits as the measurement having the
fewest decimal places (counting from left to right). For example,
100 (assume 3
figures) = 123.643,

significant

figures)

23.643

(5

significant

which should be rounded to 124 (3 significant figures). Note, however, that

it is possible two numbers have no common digits (significant figures in the
same digit column).
(2) In multiplication and division, the result should be rounded off so as to
have the same number of significant figures as in the component with the
least number of significant figures. For example,
3.0 (2 significant figures ) 12.60 (4 significant figures) = 37.8000
which should be rounded to 38 (2 significant figures).

RULES FOR ROUNDING OFF NUMBERS:

(1) If the digit to be dropped is greater than 5, the last retained digit is
increased by one. For example,12.6 is rounded to 13.
(2) If the digit to be dropped is less than 5, the last remaining digit is left as
it is. For example,12.4 is rounded to 12.
(3) If the digit to be dropped is 5, and if any digit following it is not zero, the
last remaining digit is increased by one. For example,12.51 is rounded to 13.
(4) If the digit to be dropped is 5 and is followed only by zeroes, the last
remaining digit is increased by one if it is odd, but left as it is if even. For
example,11.5 is rounded to 12, 12.5 is rounded to 12.
This rule means that if the digit to be dropped is 5 followed only by zeroes,
the result is always rounded to the even digit. The rationale for this rule is to
avoid bias in rounding: half of the time we round up, half the time we round
down.

GENERAL GUIDELINES FOR USING CALCULATORS:

When using a calculator, if you work the entirety of a long calculation
without writing down any intermediate results, you may not be able to tell if
an error is made. Further, even if you realize that one has occurred, you may
not be able to tell where the error is.
In a long calculation involving mixed operations, carry as many digits as
possible through the entire set of calculations and then round the final result

appropriately. For example,

(5.00 / 1.235) + 3.000 + (6.35 / 4.0)=4.04858... + 3.000 +
1.5875=8.630829...
The first division should result in 3 significant figures. The last division
should result in 2 significant figures. The three numbers added together
should result in a number that is rounded off to the last common significant
digit occurring furthest to the right; in this case, the final result should be
rounded with 1 digit after the decimal. Thus, the correct rounded final result
should be 8.6. This final result has been limited by the accuracy in the last
division.
Most modern calcualtors allow you to carry all the results of intermediate
calcuations in the display when performing a complex series of calcuations.
By doing this, you can retain the results of each individual calculation step,
and avoid having to re-enter intermediate results (a practice that may
encourage rounding too soon). In this manner, you can completely avoid
truncation errors introduced by rounding intermediate results.
Warning: carrying all digits through to the final result before rounding is
critical for many mathematical operations in statistics. Rounding
intermediate results when calculating sums of squares can seriously
compromise the accuracy of the result.

SAMPLE PROBLEMS ON SIGNIFICANT FIGURES:

Instructions: print a copy of this page and work the problems. When you are
ready to check your answers, go to the next page.
1.

37.76 + 3.907 + 226.4 = ?

2.

319.15 - 32.614 = ?

3.

104.630 + 27.08362 + 0.61 = ?

ANSWER
KEY
TO
SAMPLE
SIGNIFICANT FIGURES:
1.

37.76 + 3.907 + 226.4 = 268.1

PROBLEMS

ON

2.

319.15 - 32.614 = 286.54

3.

104.630 + 27.08362 + 0.61 = 132.32

Q.4 STANDARD DEVIATION:

Definition:

It is defined as the square root of the means of square of individual

deviation.
It is denoted by S.
Where S is the standard deviation for observation less than 20.
When number of observations are more than 20, the term (sigma) is used
and it is defined as

OR
The Standard Deviation is a measure of how spread out numbers are.

STANDARD DEVIATION:
1-The Standard Deviation is a better way to measure variation. First, we
look at the difference between each data value and the mean:. Then, to make
sure all the distances are positive, we square that difference:. Next, we add
up these differences for all of the observations: . Finally, we divide by (n
1) and take the square root to in some way undo the squaring from before.
This gives the formula: . Standard Deviation is denoted s, and it is in the
same units as the observations in the data set.
2-The Variance is the square of the standard deviation, s2. Since its units
are in squared units of the original observations, its value is harder to
interpret than standard deviation. As a result, it is not used as much.
Example
Consider the data set 1 2 3 4 5. We see that . Lets find the range, standard
deviation, and variance.
Range = Maximum Minimum = 5 1 = 4.
To find standard deviation, we can use a table to calculate each part

separately.

Sum

xi
1
2
3
4
5
---

We see that , so:

1 3 = -2
2 3 = -1
33=0
43=1
53=2
---

4
1
0
1
4
10

Finally, the variance is .

Now, consider the data set 1 1 3 5 5. We see that again. Lets find the range,
standard deviation, and variance.
Range = Maximum Minimum = 5 1 = 4.
To find standard deviation, we can use a table to calculate each part
separately.

Sum

xi
1
2
3
4
5
---

We see that , so:

1 3 = -2
1 3 = -2
33=0
53=2
53=2
---

4
4
0
4
4
16

In this data set, the variance is . So we see that the second data set has more
variation than the first one, which makes sense. The observations are spread
further away from the mean than in the first set of data.
Some Notation
In a sample, the standard deviation is denoted s and the variance s2.
In a population, we call the standard deviation (sigma) and the variance 2
(sigma squared).
Formulas

Here are the two formulas, explained at Standard Deviation Formulas if

you want to know more:
The
"Population Standard
Deviation":
The
"Sample Standard
Deviation":
Looks complicated, but the important change is to divide by N-1 (instead
of N) when calculating a Sample Variance.
A quick note about the standard deviation formula: Often, people wonder
why we divide by n 1 in the formula instead of n, which is the number of
observations. The reason is because of something called degrees of freedom.
We already need to know the meanfor the standard deviation formula.
Therefore, if we know only n 1 of the observations, we could figure out
the last one, since the mean tells you the sum of the observations. As a
result, it turns out that dividing by n 1 will make the standard deviation an
unbiased estimator, meaning that as the sample size increases, s will not
consistently overestimate or underestimate the true population standard
deviation.
The number of significant figures roughly corresponds to precision, not
accuracy

SEEMA TAMBE
1.EXPLAIN HOW STANDARD DEVIATION (S) IS CALCULATED?
Ans: The standard deviation (S) is defined as the sum of squares of
deviations of individual measurement from the mean of the set is divided by

the number of the degree of freedom and then the square root of this term is
obtained
Standard deviation (S) is expressed as

Standard deviation (S)can be estimated from spread or range (w)of the set by
using equation
S=w/d
Where d is statistical factor
S=Standard deviation can be estimated by using equation
S=W/N
Where N is Total number of the measurement

2.Q-Test
Ans:The Q-test is one of the most statistically correct criteria used for
rejecton of doubtfull data
Scope:It doesnot require large no of measurement in the set
Applications:First arrange all the measured value of the set in their
increasing order
Find the spread or range of set thus arranged
Find difference between doubtfull measurement and its neighbouring
measurement
sDivide these difference by spread of the set
This gives Qs calculation:

T test
A statistical examination of two population means. A two-sample t-test
examines whether two samples are different and is commonly used when the
variances of two normal distributions are unknown and when an experiment
uses a small sample size. For example, a t-test could be used to compare the
average floor routine score of the U.S. women's Olympic gymnastic team to
the average floor routine score of China's women's team.

Chi 2 test
Pearson's chi-squared test is used to assess two types of comparison: tests of
goodness of fit and tests of independence.
A test of goodness of fit establishes whether or not an observed frequency
distribution differs from a theoretical distribution.
A test of independence assesses whether paired observations on two
variables, expressed in a contingency table, are independent of each other
(e.g. polling responses from people of different nationalities to see if one's
nationality is related to the response).
The procedure of the test includes the following steps:
Calculate the chi-squared test statistic, , which resembles a normalized
sum of squared deviations between observed and theoretical frequencies (see
below).
Determine the degrees of freedom, df, of that statistic, which is

essentially the number of frequencies reduced by the number of

parameters of the fitted distribution.

Compare to the critical value from the chi-squared distribution with

df degrees of freedom, which in many cases gives a good
approximation of the distribution of .

Que> In replicate analysis of a metal ore the following results are obtained
sample
% of
metals

1
40.13

2
40.11

3
40.14

4
40.10

5
40.18

6
40.16

Calculate mean, average deviation ,and standard deviation

Ans>
Mean=xi/n
=40.13+40.11+40.14+40.10+40.18+40.16/6
=40.13
Obr.
1
2
3
4
5
6

X
40.10
40.11
40.13
40.14
40.16
40.18

XX

40.13

(X-XX)
-O.03
-O.O2
0
O.O1
O.O3
0.05
O.14

(X-XX)
0.0009
0.0004
0
0.0001
0.0009
0.0025
0.0048

Average deviation =di/n =0.14/6=0.0233

Std deviation=(x-xX)/n-1
=0.0048/6-1=0.03098

Que> in this six determination of ion from samples, each of which contain
320 miligram of ion. The following results were obtained.
Sample
no
Fe(found
in mg)

120

138

158

168

162

178

Mean=xi/n
=120+138+158+168+162+178/6
=154
Median= Arrange in ascending order
120,138,158,162,168,178
=158+162/2 =160
Obr no
1
2
3
4
5
6

x
120
138
158
162
168
178

Average deviation=di/n
100/6=16.66

154

(x-x)
-34
-16
4
8
14
24
100

(x-x)
1156
256
16
64
196
576
2264

Standard deviation=(x-x)/n-1
=2264/6-1
=47.581/2.236
=21.279
Range= Xmax-Xmin
=178-120
=58
The normality of solution is determined by four separate titration .The result
being 0.1541, 0.1549, 0.1539, 0.1543 .
Calculate mean,median ,range,average deviation,relative average deviation
from mean,standard deviation,variance,coefficient of variation.
CALCULATION:
1. MEAN(x) =(0.1541+0.1549+0.1539+0.1543 )/4= 0.6172/4=0.1543
2. By arranging the observed value in ascending order we get,
0.1539, 0.1541, 0.1543, 0.1549
Since there are even number of values therefore ,the meadian is the mean of
the two middle values
MEADIAN(m) = (0.1541+0.1543)/2= 0.1542
3.RANGE = 0.1549 - 0.1539 = 0.0010
4.DEVIATION FROM MEAN = (Observed value -mean)
d1 = |0.1541 - 0.1543| = 0.0002
d2 = |0.1549 -0.1543| = 0.0006
d3 = |0.1539 -0.1543| = 0.0004
d4 =|0.1543 - 0.1543| = 0.0000
5.AVERAGE DEVIATION FROM MEAN
=(0.0002 + 0.0006 + 0.0004 + 0.0000) /4

= 0.0012 /4
= 0.0003
4.RELATIVE AVERAGE DEVIATION FROM MEAN =
( Average deviaton from mean)/Mean
= 0.0003/ 0.1543
= 0.00194
5.DEVIATION FROM MEADIAN = (Observed value -meadian )
d1 =| 0.1541 - 0.1542| = 0.0001
d2 =|0.1549 - 0.1542|= 0.0007
d3 =|0.1539 - 0.1542|= 0.0003
d4 =|0.1543 - 0.1542|= 0.0001
6.AVERAGE DEVIATION FROM MEADIAN
= (0.0001+0.0007+0.0003+0.0001) /4
= 0.0012 / 4
= 0.0003
7.RELATIVE AVERAGE DEVIATION FROM MEADIAN
= (Average deviation from meadian) /Meadian
= 0.0003 / 0.1542
= 0.00194
8.STANDARD DEVIATION i=4
=(x - x)2 =(0.0012)2 = 0.00000144
i=1
= 0.00000144 /(N -1)

=0.00000144/(4-1)
=0.00000144/3
=0.00000048

= 6.9282*10-4

9. VARIANCE = ( S)2
= (6.9282*10-4)2
= 47.9999*10-8
10.COEFFICIENT OF VARIATION
= (S / X) *100

= (6.9282*10-4 / 0.1543)*100
= (44.9008*10-4)*100
=0.4490 %