Chapter 10 - Precision and Accuracy of Chemical Analyses Flashcards

1
Q

Measurements always contain ____ and ______

A
  • errors
  • uncertainties
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2
Q

Measurement data can only give us an _______ of the “true” value

A

estimate

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3
Q

Why is estimating the reliability of experimental data is extremely important whenever we collect laboratory results?

A

because data of unknown quality are worthless

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4
Q

Results that might not seem especially accurate may be of considerable value…

A

if the limits of uncertainty are known

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5
Q

It is the best estimate of the true value

A

central value for the set

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6
Q

It is done in order to improve the reliability and to obtain information about the variability of results

A

Replicates

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7
Q

The most widely used measure of central value

A

mean

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8
Q

mean is also called as

A

arithmetic mean or average

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9
Q

Mean is obtained by

A

by dividing the sum of replicate measurements by the number of measurements in the set

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10
Q

∑xi means

A

to add all of the values xi for the replicates

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11
Q

Formula of Mean

A

x̄ = add all values for replicates / number of replicates

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12
Q

It is the middle result when replicate data are arranged in increasing or decreasing order

A

Median

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13
Q

How can you determine the median for an odd number of results?

A

by arranging the results in order and locating the middle result

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14
Q

How can you determine the median for an even number of results?

A

the average value of the middle pair is used

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15
Q

It indicates the closeness of the measurement to the true or accepted value

A

Accuracy

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16
Q

Accuracy is expressed by the ____

A

error

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17
Q

It is a measure of how close a series of measurements are to one another

A

Precision

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18
Q

Precision describes the ________ of measurements - in other words, …

A
  • reproducibility
  • the closeness of resuts that have been obtained in exactly the same way
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19
Q

Three terms used to describe the precision of a set of replicate data:

A
  1. Standard deviation
  2. Variance
  3. Coeffcient of variation
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20
Q

These three are functions of
how much an individual result xi differs from the mean, called the ________

A

deviation from the mean di

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21
Q

Deviation from the mean di formula

A

di = |xi - x̄|

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22
Q

What must be comapred to evaluate the accuracy of a measurement?

A

The measured value must be compared to the correct value

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23
Q

What must be comapred to evaluate the precision of a measurement?

A

You must compare the values of two or more repeated measurements

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24
Q

The difference between the experimental value and the accepted value

A

Error

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25
Formula of Error
Error = experimental value - accepted value
26
It is the correct value based on reliable references
Accepted value
27
It is the value measured in the lab
Experimental value
28
How can we determine precision?
just by measuring replicate samples
29
Why is accuracy often more difficult to determine?
because the true value is usually unknown
30
What must be used instead to determone accuracy?
Accepted value
31
Accuracy is expressen in term of, what?
either absolute or relatice error
32
Formula for Absolute Error
E = xi - xt
33
xi in Absolute error is...
a measurement of the quantity
34
xt in Absolute error is...
the true or accepted value of the quantity
35
often a more useful quantity than the absolute error
Relative Error
36
Formula of Relative Error
Er = xi - xt / xt x 100%
37
Relative error is also expressed in
parts per thousands (ppt)
38
Results can be _____ without being _____ and ____ without being _____
- precise, accurate - accurate, precise
39
Types of Errors in Experimental Data
1. Random (or indeterminate) 2. Systematic (or determinate) 3. Gross Error
40
It causes data to be scattered more or less symmetrically around a mean value; usually small in values and not avoidable
Random (or indeterminate) error
41
Random error
- observational error - environmental error
42
It causes the mean of a data set to differ from the accepted value
Systematic (or determinate) error
43
In general, a systematic error in a series of replicate measurements...
causes all the results to be too high or too low
44
Example of Systematic error
The loss of a volatile analyte while heating a sample
45
Systematic error
- Instrumental error - Environmental error - Observational error
46
Systematic error other examples
- Miscalibration of pH meter - Miscalibration of analytical balance - Evaporation of liquids - Spattering chemical
47
- third tye of error - usually occur only occasionally, are often large, and may cause a result to be either high or low
Gross error
48
Gross error is often a product of ____ ___
Human error
49
Gross errors lead to ____
outliers
50
Systematic errors have a ____ ___
definite value
51
Systematic errors have an ____ ___
assignable cause
52
Systematic errors are of the same magnitude for replicate measurements made in the same way, leading to _____ in measurement results
bias
53
Bias in measurement results affects, what?
- all the data in a set in the same way - it carries a sign
54
Systematic errors may be either ________ or ________
- constant - proportional
55
Magnitude of a _____ ___ stays essentially the same as the size of the quantity measured is varied
Constant error
56
With constant errors, the ____ ____ is _____ with sample size, but the ____ ____ ____ when the sample size is changed
- absolute error is constant - relative error varies
57
It increase or decrease according to the size of the sample taken for analysis
Proportional errors
57
With proportional errors, the ______ ____ ____ with sample size, but the _____ ____ stays _____ when the sample size is changed
- absolute error varies - relative error stays constant
57
It is always desirable because the response of most instruments changes with time as a result of component aging, corrosion, or mistreatment
Periodic calibration of equipment
58
Most personal errors can be minimized by
- careful - disciplined laboratory work
59
materials that contain one or more analytes at known concentration levels
Analysis of Standard Samples (or Standard Reference Materials, SRMs)
60
SRMs can be prepared by
- synthesis - purchased from a number of governmental and industrial sources
61
It contains the reagents and solvents used in a determination but no analyte
Blank
62
Many of the sample constituents are added to simulate the analyte environment, which is called the _____ ____
Sample matrix
63
As the size of a measurement ______, the effect of a constant error ______
- increases - decreases