100 tayangan

Diunggah oleh Justin Wilde

- Nonparametric Statistical Inference, Fourth Edition
- A Short Course of Time-Series Analysis and Forecasting by D S G Pollock
- 2008 - Claeskens, Hjort.pdf
- Algebraic and Geometric Methods in Statistics
- Experimental Design and Data Analysis for Biologists - Quinn & Keough - Cambridge 2002
- Statistical Analysis My Ppt
- statistical analysis
- 2009 Freedman Statistical Models RevEd
- Livingstone, Data Analysis
- Making Sense of Data a Practical Guide to Exploratory Data Analysis and Data Mining
- Research Design and Statistical Analysis
- Hidden Figures: The American Dream and the Untold Story of the Black Women Mathematicians Who Helped Win the Space Race
- The Library Book
- Elon Musk: Tesla, SpaceX, and the Quest for a Fantastic Future
- Never Split the Difference: Negotiating As If Your Life Depended On It
- Shoe Dog: A Memoir by the Creator of Nike
- The Subtle Art of Not Giving a F*ck: A Counterintuitive Approach to Living a Good Life
- Sapiens: A Brief History of Humankind
- The Unwinding: An Inner History of the New America
- This Changes Everything: Capitalism vs. The Climate

Anda di halaman 1dari 21

•

•

Analysis of Experimental Data

A Practical Guide to Data Handling and Manipulation for Students of Physical and Analytical Chemistry

. December 22, 1994

Harry A. Frank and Jane L. Knox

Department of Chemistry 215 Glenbrook Road University of Connecticut, U-60 Storrs, CT 06269-3060 USA

•

TABLE OF CONTENTS

•

I. INTRODUCTION ..•..........•..............•...................................••.•.... ~ ...•..•••..••.•••.•••••••••••••.••.•••• 2

A. ACCURACY - 2

B .. DETERMINATE ERRORS AND ACClIRACY _ · 3

C. INDETER.\1INATE ERROR AND·PRECISION : _ ...•....•.. 3

II.' UNCERTAINTY 4

A. STANDARD DEVIATION ;.. _4

1. Derivation of the Expression for Standard Deviation .4

2. Calculation of the Standard Deviation _ 6

B. AVERAGE DEVIATION _ 7

C. RANGE _ _ 7

D. THE GRADUATION METHOD· - 8

E. UNCERT AlNTIES INHERENT IN GRAPHIl"G : _ 8

III. PROPAGATION OF ERROR ~ 9

A. EXPRESSIONS DERIVED BY DIFFERE:-JTIAllOS _ 10

B. EXPRESSIONS DERIVED BY THE "WORST CASE" ~ETHOD _ 12

IV. SIGNIFICANT FIGURES 1-'

A. ROUNDING OFF , _._ 14-

B. WHICH ZEROS ARE SIGNIFICANT? _ 15

C. THE THREE Al'lD THIRTY RULE _ I 5

D. SIGNIFICANT FIGURES FROM UNCERT Alr-.TY OF SINGLE MEASUREMENTS 16

E. SIGNIFICANT FIGURES FROM STANDARD DEVIATION : 18

•

•

L Introduction

A. Accuracy

When a quantitative value is determined experimentally, our main concern is that we obtain the "right" answer. The comparison between our experimentally determined value and the true value is a measure of accuracy.

Definition: Accuracy is the degree, of agreement between the experimental value and the true value.

The accuracy has a sign associated with it and that sign indicates whether the experimental value is high (+) or low (-) with respect to the true value.

Example:

A solution known to have a pH of 8.00pH units is measured with a pH meter and

the average of several trials is found to be 7.90 pH units. '

The accuracy is 7.90 pH units -8.00pH units = -0.10 pH units,

•

This gives an absolute error because the units of the error are the same as the units of the measurement. A relative error can also be calculated with respect to the true value:

_ O.lOpH units x 100= -1.3%

8.00pH units .

Note that the relative error is unitless.

The accuracy can only be measured if the true value is known which is not always the case; someone has to have found it in the first place by some method. Different methods might inherently give slightly different answers. Which method will ultimately be used to provide the "true" answer? Even standards change occasionally as the ability to make certain types of measurements change. Up until 1948 the coulomb was' defined a. .. the quantity of electricity which must pass through a circuit to deposit 0.0011180 grams of silver from a solution of silver nitrate. Now it is defined as the quantity of electricity on the positive plate of a condenser of one farad capacity when the electromotive force is one v olt,

We will not deal here with the problem of what is 1.'1e true value. You should be aware, however, that it is not as straightforward as you might have thought. For that reason, perhaps accepted value is a better term.

•

,

•

•

•

B.

Determinate Errors and Accuracy

What is it that keeps every measurement or analysis from being completely accurate? That is, what causes the discrepancy between the accepted value and the measured value? The discrepancy is caused by many small deviations which can be divided into two groups: determinate and indeterminate errors.

Definition: Determinate errors are errors which have a definite value that can, in principle, be measured and accounted for.

Determinate errors, also called systematic errors, can be divided into arbitrary categories. The most common divisions are instrumental, operator; and method errors. Determinate errors are often unidirectional, that is they are all positive or all negative with respect to the accepted value. Be aware that determinate errors can be corrected for but . only after the cause is determined. This might take some detective work. For example, an incorrectly calibrated instrument might give results which are too high; this determinate error would be the fault of the operator. On the other hand, an instrumentsignal drifting downward might give a low value and illustrates instrumental error.

C. Indeterminate Error and Precision

Even when all determinate errors are corrected and compensated for, the same measurement taken several times will not necessarily give the same answer. This is because of indeterminate errors also called random or statistical errors.

Definition: Indeterminate errors are errors which fluctuate randomly and do not have a definite value; They cannot be. positively identified.

To further understand indeterminate errors, consider the weight of an object obtained by doing five different weighings on a four place analytical balance.

trial I: trial 2: trial 3: trial 4: trial 5:

0.7952 g 0.7950 g 0.7951 g 0.7953 g 0.7951 g

The first three figures are the same in all cases. The last figure has an uncertainty associated with it. This uncertainty isa function of the type of sample, the conditions under which it is being weighed, the balance, and the person doing the weighing. Even when all factors are optimized, there will still be some variation in the weight. This variation or uncertainty is the result of pushing the balance to its limit.

We could cut the last figure off; then all the weights would be the same, but the weight would be known only to the nearest milligram. We obtain more information if we

3

keep that last figure but remain aware of its uncertainty. That uncertainty arises because of •

indeterminate error; and is indicative of the precision of the measurement.'

Definition: Precision is the degree of agreement between replicate measurements of the same quantity.

Note that even if the precision of a measurement is excellent, the value obtained can have poor accuracy if there has been a determinate error. For example, an incorrectly calibrated instrument cannot give an accurate reading although the precision very likely will not be affected. On the other hand, poor precision rarely results in an accurate value being obtained.

n, Uncertainty

The element of uncertainty in experimental data can be quantified and is often reported along with the actual experimental value itself. The value of the uncertainty gives one an idea of the precision inherentin a measurement of an experimental quantity. So important is the concept of uncertainty it actually has a principle named after it.! With the uncertainty being reported along with the experimental quantity one has an idea of how "good" the reported experimental value is. Consequently, comparisons of the numbers obtained in a series of measurements with the same or different techniques are made more

. meaningful by the inclusion of uncertainties.

There are many ways to quantify uncertainty, ranging from very simple techniques •

to highly sophisticated methods. The method used will depend upon how many

measurements of a single quantity are made and on how crucial the reporting of the value

of uncertainty is with regard to the interpretation of the experimental data. The following is

a list of many of the ways in which uncertainty is reported.

A. Standard Deviation

1. Derivation of the Expression for Standard Deviation

The most widely used method for calculating uncertainty is representing it by the standard deviation of a series of measurements. This can be easily accomplished if it is assumed that a gaussian distribution function best describes the spread in the error values for a series of measurements made on a single observable. The distribution function is then termed a "normal" error probability function and written

I The influence of indeterminate error on accuracy is related to the confidence limit of a measured value; this topic is dealt with in the analytical chemistry courses.

•

~ The uncertainty principle is a fundamental concept of the quantum mechanics giving the ultimate precision with which simultaneous measurements of experimental quantities can be made.

4

•

where e represents the error in a measurement (negative or positive) and (J' isa parameter known as the standard deviation. One can see from this equation that (J' is related to the width of the distribution of errors. If (J' has a small value, the probability function decreases rapidly from its maximum value (where e =0) indicating that the probability of large errors in the measurement is .small, If a has a large value, the probability function is broad indicating a high degree of probable error in the measurement. Mathematically (J' is defined as the root-me an-square error associated with this probability function.

[ ]"2

_ [ 2] 1/ 2 _ I J+ 00 2 - c~ 12a~ d

(]'= E - ~ e e E

(J'-v2Tr -00

where e 2 is the mean of the squared errors. If each individual error, Ei is known exactly (through knowledge of the true value of the observable) an approximate formula for (J' can be derived; it is given by

[ ]"2

(J'= .!. i»

n i=1

•

where n is the number of independent data or degrees of freedom on which the calculation of o ls based, and e, is the difference between the observed value and the true value of a

quantity (i.e., E;= Xi - Xrrv~ ).

In a typical experiment one would not know the true value of an observable (or why do the experiment"). A goodapproximation to the true value of an observable is the arithmetic mean, X, of a series of n measurements (neglecting systematic error),

1 " X::- LXi

n ;=1 .

where the x; are the values for the individual measurements. Because it is known that the sum of an entire set of deviations from the mean must necessarily add up to zero, i.e .•

"

I,(x;-x) =0

;=1

•

then a knowledge of only n-I values of x; is necessary to define the nth or last value. That is any value x; can be determined from the remaining Xi values provided the mean x has been calculated. Thus, it is found that calculating the mean value, x, reduces the number of independent variables or degrees of freedom with which one can determine the precision inherent in a series of measurements .

5

The problem of determining the uncertainty (which is a measure of precision) in a •

series of measurements of a single observable by the standard deviation method is solved

by using the formula

[ ]1/2

1 n ,

s= -I(x;-xf

n-l,=l

where s2 is termed the variance, and the n-l· term in the denominator follows from the . above ·discussion. This represents the best estimate ofthe standard deviation for a finite Set of data. Note that E; is being approximated by x; -x , hence n-l appears in this equation.

2. Calculation of the Standard Deviation

The standard deviation of a set of five weights can be calculated as.shown:

x;-x

0.7962 0.7950 0.7941 0.7953 0.7955

0.0010 -0.0002

-0.0011

0.0001 0.0003

1.0 x 10-6 4.0 x 10-8 1.2 x 10-6 1.0 x 10-8 9.0 x 10-8

•

1. I,x;=3.9757 0.79522=x

5 ;=1 . 5

[ S ]1' ~ [ . J" 2

-( _l-L(X;-X)~ . = _!_(2.35xlO~) =5

n-l) ;=1 4.

s=7.7 x 104=0.0008

Note that the standard deviation has the same units as the measurement itself, i.e., g. and is thus a measure of absolute precision. The number of figures used to express x and 5 is explained in Section N, Significant Figures:

The standard deviation can be expressed relative to the mean giving a measure of relative precision. Relative precision can be expressed as a fraction, a percentage, pans per thousand, or any other desired relative measure. When it is expressed as a fraction, it is usually referred to as the coefficient of variation. .

0.OOO8g 0.00 10 coefficient of variation 0.7952g

•

6

•

0.0008g .

--.....;;.. x 1000=1.0 parts per thousand 0.7952g

Notice that the relative error is a unitless number.

B. A verage Deviation

Sometimes to get a quick estimate of the uncertainty or precision, it is easier to use the average deviation. The average absolute deviation is simply the mean of the sum of the deviation of individual trials from the mean without regard to sign (if the sign were taken into account, the sum of deviations would of course be zero).

I,lx.-xj

average absolute deviation = I

. n,

In the case of the weights which we have been looking at, the average absolute deviation is:

0.0010+0.0002+ 0.0001+0.0003 0.0027

=---

5 5

average absolute deviation=0.OOO5

•

The average absolute deviation is a measure of absolute uncertainty because it is in the same units as the measurement, because it is calculated from the absolute values of the

deviation. •

The average relative deviation usually measured in parts per thousand (ppt) is: . }::IXi *1000- 0.0005 x 1000~O;6ppt

x 0.7952

The average absolute and relative deviations are slightly smaller than the corresponding standard deviations, but they are still reasonable estimates of the magnitude of uncertainty.

C. Range

When a series of measurements is made on a single observable, the uncertainty can be crudely approximated by the range, which is given as the difference between the maximum and minimum values of the measured quantity. In the case of the set of five weights given in Section I. C., the range is 0.7953 g - 0.7950 g = 0.0003 g .

•

7

D.

The Graduation Method

•

When a measurement is done only once or when it is not possible to repeat an experiment enough times for a statistical treatment to be used, the uncertainty must be approximated. Very often the uncertainty in a single measurement is given by a value onehalf of the smallest level of graduation in the measuring instrument. For example. if a single measurement of the length of an object is to be made using a meter stick marked with millimeter graduations, the length should be reported±.5 nun (or ±.OOO5 m).

In some cases. it may be possible to divide the space between scale divisions into five equal parts. For example, a pH meter usually is calibrated in tenths of a pH unit but is . read to 0.02 pH units.

0.0677 :i: 0.0005 meters

0 2 3 4 5 6 7 8 9 10

Centimeters •

6.76 ::I: 0.02

I: ,J

I I I I I I I ! ,

6 7 8 9 10

pH You must use your own judgment in choosing an increment to calculate the precision using the Graduation Method. If in doubt, always be conservative; i.e. report the largest of possible uncertainties.

E. Uncertainties Inherent in Graphing

When graphical techniques are used to determine a quantity of interest, special methods are needed for determining the uncertainty in the measurement of the quantity. The method to be used depends on the number of observations (data points) used to determine the quantity of interest. In all cases the ranges of data points should span the graph sufficiently to illustrate the experimental behavior with clarity. A distinction here is

(arbitrarily) made between a small number of data points (less than 10) and a large number •

of data points (greater than 25). For situations in-between subjectivity.is required to make

a choice of the following two methods:

8

•

1. Method of Limiting Slopes

When few observations are made, the "method of limiting slopes" is the best technique for determining the uncertainty in the measurement of the slope and intercept of a linear plot. The technique consists of drawing a rectangle around every data point where

the dimensions of the rectangle represent the uncertainties. of the measured quantities. A best straight line is then drawn throughout the individual points. Two other lines which represent the maximum or minimum slopes are then drawn so that both lines pass through every rectangle. The differences in the slopes or intercepts of the limiting lines can be taken as twice the uncertainty in the slope or intercept of the best line. The following figure produced by C. David illustrates the procedure.

y

•

high

error iny

reported low

error..... oGIIf--

Inx If 1

x

2. Limiting Slopes Method Consistent with Scatter in the Data

When a large number of observations is made, an estimate of the uncertainty in the intercept can be made from the scatter in the data. The two lines corresponding to the limiting slopes can be drawn so as to remain within the scatter of points. The uncertainties

in the slope or intercept of the best line is thus straightforwardly obtained. .

ill. Propagation of Error

Because of the impossibility of measuring an experimental quantity to infinitely small precision, there will always exist random error. When the quantity of interest is directly measurable, anyone of the techniques set forth in Section II can be used to estimate the precision of the experimental measurement. When the quantity of interest is

•

9

not directly measurable but results from a calculation involving two or more •

experimentally determined quantities, it is necessary to determine how the error in each

individual quantity propagates through to the final result. This concept of the propagation

of errors is important in determining ways of improving experimental design. For

example, it would be a waste of money to buy an expensive analytical balance to replace an

ordinary trip scale if the uncertainty in the weight of a sample contributes insignificantly to

the precision or accuracy of the final result.

A. Expressions derived by differentiation

We designate the quantity of interest as x, where x is understood to be a function of more than one experimental quantity (independent variable),i.e.,

x= [(a,b,c ... )

where a, b, c ... are the measured quantities. (Strictly speaking x is only proportional tofin that x may result from a calculation involving nonrneasurable quantities, e.g. n: or h. For simplicity, we ignore this finer point.) These independent variables, a, b. c. have corresponding differential changes da. db, dc.... From the chain rule we have

(ax) (ax) (ax)

dx= aa da+ab db+ ac dc+ ...

•

If it is assumed that the uncertainties ~a, tsb, Sc.«. of the individual experimental determinations are reasonably small then it is possible to write

There is a problem, however, in that the uncertainties Sa, Sb, Sc .... come as positive .nd negative quantities for random errors. For systematic errors where the exact values (and signs) of the uncertainties are known, one uses the above expression for ~ for the propagation of the error. For the case of random error, the ambiguity is removed by considering the square of the above expression for ~. Thus, it is found

(!\x)' = (;=)' (&.)' +( ;~)' (61))' + (~~)' (Ile)' + ... +2(~:)(~~)~aM+ ...

Averaging this expression over all possib le values ~a, M, ~c,.,. yields

•

10

•

because the average values of D.a,M,D.c ... will always be zero for a normal gaussian distribution of errors; i.e., the frequency of positive deviations equals that of negative deviations. In particular, therefore, the above expression suffices for use in the determination of the absolute error propagated through a calculation. The relative error is found by dividing .1x by x.

Examples:

1. x=a+b

2. x=a+b

•

Llx=[(1)\&z)2 +(_1)2(M)2 I" =[(6a)2 +(M)2]"2

These formulas were obtained by taking partial derivatives as shown above. Notice that the absolute error ofa value obtained by either addition or subtraction is the same; the square root of the sum of the squares of the absolute error of each individual measurement. This means that we want to minimize absolute errors when a result will be obtained by addition or subtraction of measurements.

3. x=axb

This gives an expression for the absolute error of a product of two variables.

It is interesting to manipulate this equation to obtain the relative error, Sx] x

Realizing that b = x/a and a = xIb, we obtain:

But this is simply:

'.

I I

This gives us the result that the relative error of a product is the square root of the sum of the relative errors of the variables .. This means that we want to minimize relative errors when a result will be obtained by multiplication of measurements.

4.

a x=-

b

This gives the expression for the absolute error of a quotient of two variables.

Let us once again manipulate this equation to obtain the relative error of the resulting value, .1x.

x

since

1 x a x -=- and --=--

b a b2 b '

then

This is a very interesting result; although the absolute error of the result of a

. quotient is very different from that ofa product, the expression for the relative error of a result obtained from the quotient of the two measurements is the same as that of a result obtained from the product of two measurements. Thus, once again we. want to minimize relative errors when a result will be obtained by division of one measurement by another.

The reader might want to derive the expression for absolute and relative errors in the case of an exponential relationship, x = an , and in the case of a logarithmic relationship, x=loga.

B. . Expressions derived by the "worst case" method

The formulas presented above are useful forthe propagation of error from measured quantities throughto the quantity of interest. A less rigorous approach to error

•

•

•

12

•

•

•

propagation presented by Gordon et al.' can be achieved by examining the result of an arithmetic operation in the limits of the uncertainties of the variables upon which the quantity of interest depend. The idea is to deduce the uncertainty of a result of an operation by expo ring the high and low limits of the result using the ranges imposed by the precisions in the independent variables.

The following figure shows two observables, a and b, and their respective uncertainties, Sa and M. The "worst case", highest value of a is a + Sa, and its lowest value is a -!la. The "worst case", lowest value of b is b - M, and its highest value is b.+ M. The figure shows that, for example, if the quantities a and b are added, the uncertainry in the result, x = a + b, will be bound on the high side by (a + 6.a) +(b + MJ) and on the

. low side by (a - 6.a) + (b - M). The difference between these two limits gives 'two times the uncertainty, Sx. This argument can be extended to all arithmetic operations. The expressions for addition, subtraction, multiplication and division are given below.

------(a+~a) + (b+ilb) . upper bound

x= a+b

"-----f--(a-~a) + (b-ilb) lower bound

a

b

J Gordon. R .• Pickering. M. andBisson, D. J. Chem. Ed .• 61. 780 (l984).

13

Examples: •

-1. ,x=a+b

26x=[(a + ~a) + (b + L\b)] -[(a - ~a) + (b- M)]

2. x=a-b

26x = [( a + M) ., (b - Sb )] - [( a - ~a) - (b + M)]

3. x~axb

26x=[(a + M) x(b + L\b)]-[(a - M) x (b- M)]

a

4. x=-

b

26x=[ a +~aJ-[ a - ~J

b-M b+L\b

IV. Significant Figures •

A. Rounding off When rounding off a number, the figure in the place immediately preceding the dropped figure remains the same if the dropped figure is less than five and is rounded up If the dropped figure is greater than five.

Example:

45.243 ~ 45.24

712.97 ~ 713.0

0.736 ~ 0.74

If the dropped figure is five, then the general rule is that the preceding figure is treated in such a way as to make it an even number. This means that half the time the preceding figure remains the same (if it is even) and half the time it is rounded up (if it is odd).

Example:

2.75 ~ 2.8

•

89.625~89.62

14

•

B.

Which Zeros are Significant?

First, let us make sure we know how to count significant figures. The biggest confusion arises with zeros.

1. Zeros to the right of the decimal point but to the left of the first non-zero digit are

not significant. They are place keepers and can be eliminated by using exponential notation.

Example:

0.000151

3 significant figures

1.51 X 10-4

3 significant figures

2. . Zeros to the right of a non-zero digit mayor may not be significant; at times it

requires judgment to decide on their status. It is best to use exponential notation to avoid ambiguity.

Example:

54.20

4 significant figures: the value is understood to be between 54.19 and 54.21.

•

17,000

All three zeros are probably not significant.

1.7 x lQ4

Two significant figures. Exponential notation clears up any ambiguity.

C. The Three and Thirty Rule

In dealing with significant figures in subsequent sections, we are going to make use of a somewhat arbitrary rule having to do with uncertainties.

This rule can be stated as follows:

The numerical value of the uncertainty of a calculated value must be between three and thirty disregarding the decimal point.

Examples:

1. A concentration is calculated using Beer's Law and found to be 52.77 mg/L.

•

A. Suppose the uncertainty is found to be 0.13 mgIL. Since 13 is between 3 and 30. the uncertainty can be taken as shown. The concentration is then expressed as 52.77 ± 0.13 mg/L.

I .

15

B. Suppose the uncertainty is found to be 0045 mg/L. Since 45 is not between 3 and 30. the uncertainty is rounded to 0.4 mg/L because 4 is between 3 and 30. The concentration is then expressed as 52.8 ± 004 mg/L.

•

D. Significant Figures from Uncertainty of Single Measurements

Definition: Significantfigures are figures needed to report a value to the precision with which a measurement is made.

The concept of significant figures arises only when we begin to talk about measurements. It has no meaning with respect to pure numbers. That is why nobody ever worries about significant figures when doing long division in third grade arithmetic; the quotient 3.8948/41.65 can be carried out as far as we want but in finding the quotient 3.8948 g141.65 mL we must be concerned about the precision of each measurement.

The question we want to answer is to how many figures should the quotient be expressed? In order to answer this. we must know the precision of the measurements and from those propagate the uncertainty of the resulting quotient. .

For the purpose of this example, we will assume that the mass had a precision of ±. 0.0004 g. and the volume had a precision of ± 0.04 mL. Remember from the propagation of error derivations, when x = alb, then:

llx=[ G)' (<\a)' +( - :)' (db)' r •

~ =[( ~)' +( ~)'r

llx=X[( ~)' +( ~)'r

In this case, the quotient, alb, read from the calculator is:

x

3.8948g -0.0935126_L 41.65mL mL

~= CO.0935126_L)[(0.0004)2 +( 0.04 )2]"2

mL 3.8948 41.65

.1x=0.0935 126(9.658 X 10-4)

&=9.03 x10-s = 9 x 10-s

•

16

•

By the "three and thirty" rule, the uncertainty or precision of the quotient is ± 0.00009, and any figures past the fifth decimal place are not significant. Thus, the quotient

can be expressed as: .

0.09351 ± 0.00009

By the rule of thumb, which you probably learned in freshman chemistry, we would have guessed that the number could be expressed to four significant figures because the number in the calculation containing the least figures had four. But we could riot have guessed the value of the uncertainty which is quite high, ± 0.00009 to be exact. which tells us that the last figure, 1. is not very precise at all. .

Let us look at the precision of a sum. Suppose ten aliquots of solvent are delivered' into a beaker from a pipette which delivers 25.00 ± 0.05 mL. What is the total volume . delivered?

We are adding ten pipettes so:

•

by error propagation

[ . 2 2 2]1/2

&= (0.05) +(0.05) + .... (0.05)

&=...)0.025 =0.158

&=0.16

by the "three and thirty" rule

x=250.00±0.16mL

Again, this obeys the "freshman chemistry" rule of thumb for significant figures of a sum which says that the number of decimal places in the sum is that of the addend with the least number of decimal places. Again, however, the rule does not give us the quantity of the uncertainty. In this case, the two figures after the decimal point are uncertain .

•

.17

E.

Significant Figures from Standard Deviation

•

Often in the lab multiple determinations of some value are obtained and a standard deviation is found. The standard deviation is a measure of precision and indicates the significance of the figures obtained in a mean.

Suppose the concentration of Hel is determined in triplicate with the following results:

0.052792 moles/liter 0.052817 moleslliter 0.052835 moles/liter

. x .

x= I, zi: =0.052815 moleslliter n

s = 0.000022 moleslliter

Thus, the mean is expressed to five significant figures. Note that by the "3 and 30" rule, the standard deviation is expressed as 0.000022 moleslliter and not 0.00002

moleslliter. .

•

There is a problem as to how much to round off a calculation before determining the mean and standard deviation. Looking at the three trials, the first three figures are identical, 0.0528, which means the calculation has to be carried out to at least one more place to even see an uncertainty. However, even the fourth digits do not span a really wide range: 79..,83 is a range of 4.

As a rule of thumb, if the range of the. uncertain figure is less than 6, keep another figure after the first uncertain one for the calculation of the mean and standard deviation.

If we had kept only four figures, we would have obtained the following:

0.05279 moleslliter 0.05282 moleslliter 0.05284 moles/liter

x = 0.05283 moleslliter

s = 0.000025 moleslliter

reported as x± s or in this example 0.05283 :£0.000025 moleslliter ..

The uncertainty goes out to the sixth decimal place (by the "3 and 30" rule) yet the . individual trials were only carried out to five decimal places. The mean must be expressed' to the same precision as the uncertainty; otherwise we are not getting the full value of our measurements!

•

18

•

Note that the rounding off of individual values too soon also resulted in a different standard deviation. When in doubt, it is better to keep an extra figure until the standard deviation is found; it will then tell you if you have to round off. Whenever several trials are done, a standard deviation should be used to determine the number of significant figures rather than a propagated error as shown in Section IV.D .

•

•

19

Mass

•

--------------------------------------------------------------------------

Length 1 m = 100 em = 1000 mm = 100 micronsfmu) = 1010 Angstrom

= 39.37 in - 3.2808 ft - 1.0936 yd - 0.0006214 mile

1 ft - 12 in - 1/3 yd - 0.3048 m - 30.48 em

--------------------------------------------------------------------------

=28317 em3

Volume 1 mj = 1000 liter = 100 emj = 100 ml

= 35.3145 ftj = 220.83 imperial gallons = 264.17 gal

- 1056.68 qt

1 ftj = 1728 in:'; = 7.4805 gal = 0.028317 m:'; = 28.317 liter

--------------------------------------------------------------------------

1 Ibf = 32.174 Ibm ft/(see2) = 4.4482 N = 4.4482x10~ dynes

Force 1 N = 1 (kg-m)/(see1.) = 10' dynes = 10' (g-em)/(see2) = 0.22481Ibf

Pressure 1 atm = 1.01325x105 N/(m2) [Pascal] = 101.325 kPa = 1.01325 bars

= 29.932 in Hg

= 1.01325x10o dynes/(em1.) =760 mmHg = 10.33 m water

= 14.696 Ibf/(in1.) (psi) = 33.9 ft water

Energy 1 Joule = 1 Newton meter = 107ergs = 10/dyne em

= 2.778xlO-7kW-hour = 0.23901 cal

= 0.7376 ft-lbf = 9.486x10-4Btu •

to e.v. kcal/mol em-l see-l erg

from

e.v. 1 23.05 8.065x10:'; 2.43x1014 1.60 Ix 10-11.

keal/mol 4.345x10-2 1 350 1.05xlOlj 6.95xlO-l4

em-l 1.24xlO-4 2.858x10-j 1 3xlO1V(e) 1.986xl0-H>(hc)

sec"! . 4.13xl0-l~ 9.52x10-l4 3.33xlO-11 1 6.627x 10-1.1 (h)

erg 6.25xlOll 1.439x10l3 5.04xlOl5 1.51x1026 1 -----------------------------------------------------------------------------------------------------------------

NA~ogadro = 6.02486x1023 R = NAv k == 0.0821 liter-atm/tmol OK) e = 4.80286x10-lOe.s.u. e = 299793.(3) km/see

meleetron = 9.1055x10-28gram mproton = 1.67312x10-24gram

k = 1.38033xlO-16ergs/Kelvin Ryoo = 109,737.31573(3) crrr l

•

- Nonparametric Statistical Inference, Fourth EditionDiunggah olehMario Balderas
- A Short Course of Time-Series Analysis and Forecasting by D S G PollockDiunggah olehJoanna Solik
- 2008 - Claeskens, Hjort.pdfDiunggah olehLucas Barberis
- Algebraic and Geometric Methods in StatisticsDiunggah olehjuntujuntu
- Experimental Design and Data Analysis for Biologists - Quinn & Keough - Cambridge 2002Diunggah olehDan Zach
- Statistical Analysis My PptDiunggah olehYasmin Sharma
- statistical analysisDiunggah olehnaveedsidhu
- 2009 Freedman Statistical Models RevEdDiunggah olehgerardesede
- Livingstone, Data AnalysisDiunggah olehchemistj
- Making Sense of Data a Practical Guide to Exploratory Data Analysis and Data MiningDiunggah olehbinunair_66
- Research Design and Statistical AnalysisDiunggah olehapi-3716467