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Uncertainties Salters A2 1

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Page 1: Uncertainties Salters A2 1. 2 Salters B There is guidance as to what the error is acknowledged to be if it is not stated on the apparatus It is generally

Uncertainties

Salters A2

1

Page 2: Uncertainties Salters A2 1. 2 Salters B There is guidance as to what the error is acknowledged to be if it is not stated on the apparatus It is generally

2

Salters B

There is guidance as to what the error is acknowledged to be if it is not stated on the apparatus

It is generally taken to be the smallest unit on the scale being used

eg if a balance weighs to 0.01g the error uncertainty is taken as +/- 0.01g

Salters B

There is guidance as to what the error is acknowledged to be if it is not stated on the apparatus

It is generally taken to be the smallest unit on the scale being used

eg if a balance weighs to 0.01g the error uncertainty is taken as +/- 0.01g

Page 3: Uncertainties Salters A2 1. 2 Salters B There is guidance as to what the error is acknowledged to be if it is not stated on the apparatus It is generally

Uncertainty Variation – Why?

• Example:

• Electronic set top balance • Reading is 2.05g• What range of values could it actually be?

3

Page 4: Uncertainties Salters A2 1. 2 Salters B There is guidance as to what the error is acknowledged to be if it is not stated on the apparatus It is generally

4

Deciding on precision – Volumetric glassware

CLASS: Class B has twice the tolerance of class A

CLASS: Class B has twice the tolerance of class A

Maximum volume/cm3Maximum volume/cm3

Tolerance / ± xcm3

Tolerance / ± xcm3

Temperature for true volumeTemperature for true volume

Flask

Graduated pipette

StandardStandard

Page 5: Uncertainties Salters A2 1. 2 Salters B There is guidance as to what the error is acknowledged to be if it is not stated on the apparatus It is generally

5

Volumetric equipment – class B

Flasks:Flasks:Capacity/ cm3 Accuracy limit / ±

cm3

5, 10 0.0515 0.06

20,25 0.0850 0.12

100, 250 0.20500 0.50

Standards: DIN, ISO and BS) BS1792:1982(93)http://www.reagecon.com/TechPapers/volumetricglassware.pdf

Page 6: Uncertainties Salters A2 1. 2 Salters B There is guidance as to what the error is acknowledged to be if it is not stated on the apparatus It is generally

6

Volumetric equipment – class BBulb pipettes:Bulb pipettes: Capacity/ cm3 Accuracy limit / ±

cm3

1 0.0162 0.025 0.03

10 0.04 25 0.0650 0.10

Standards: One Mark Bulb pipettes: DIN, ISO, BS)(ISO648)http://www.reagecon.com/TechPapers/volumetricglassware.pdf

Page 7: Uncertainties Salters A2 1. 2 Salters B There is guidance as to what the error is acknowledged to be if it is not stated on the apparatus It is generally

7

Volumetric equipment – class BGraduated pipettes:Graduated pipettes: Capacity/ cm3 Accuracy limit / ±

cm3

1 0.0125 0.06

10 0.1025 0.20

Standards: Graduated pipettes:(USP, DIN, ISO, BS)(ISO835http://www.reagecon.com/TechPapers/volumetricglassware.pdf

Page 8: Uncertainties Salters A2 1. 2 Salters B There is guidance as to what the error is acknowledged to be if it is not stated on the apparatus It is generally

8

Volumetric equipment – class B

BuretteBuretteCapacity/ cm3 Accuracy limit / ±

cm3

10 0.04025 0.0650 0.10

100 0.26

http://www.titrations.info/pipette-burette

Page 9: Uncertainties Salters A2 1. 2 Salters B There is guidance as to what the error is acknowledged to be if it is not stated on the apparatus It is generally

9

Volumetric equipment – Calculated example

The uncertainty associated with a grade B 25 cm3 pipette is 0.06 cm3 or 0.24% . This is calculated as follows:

The uncertainty associated with a grade B 25 cm3 pipette is 0.06 cm3 or 0.24% . This is calculated as follows:

%24.0%100cm 25

0.06cm

100%x valueEffective

Tolerance

3

3

x

Page 10: Uncertainties Salters A2 1. 2 Salters B There is guidance as to what the error is acknowledged to be if it is not stated on the apparatus It is generally

10

For a 250 cm3 volumetric flask the uncertainty is 0.20 cm3.For a 250 cm3 volumetric flask the uncertainty is 0.20 cm3.

%080.0%100cm 250

0.20cm

100%x Value Effective

yuncertaint Absolute

3

3

x

Volumetric equipment

Page 11: Uncertainties Salters A2 1. 2 Salters B There is guidance as to what the error is acknowledged to be if it is not stated on the apparatus It is generally

11

For volume measurements, the precision of a 25 cm3 measuring cylinder is 0.1 cm3:For volume measurements, the precision of a 25 cm3 measuring cylinder is 0.1 cm3:

0.25% 100%x cm 20

cm 0.05%

3

3

U

Eg for 20cm3 of a solution:Eg for 20cm3 of a solution:

100%x Value Effective

Precision21

Measuring Cylinder

Page 12: Uncertainties Salters A2 1. 2 Salters B There is guidance as to what the error is acknowledged to be if it is not stated on the apparatus It is generally

e.g. for 1.27g of iodine:e.g. for 1.27g of iodine:

12

For mass measurements, the precision of a 2d.p. balance is 0.01g:For mass measurements, the precision of a 2d.p. balance is 0.01g:

0.394% 100%x 1.27g

0.005g% U

100%x valueEffective

Precision 21

Mass

Page 13: Uncertainties Salters A2 1. 2 Salters B There is guidance as to what the error is acknowledged to be if it is not stated on the apparatus It is generally

13

Total % uncertainty =

% U of mass or% U of volume (measuring cylinder or pipette)+ % U of volumetric flask

Total % uncertainty =

% U of mass or% U of volume (measuring cylinder or pipette)+ % U of volumetric flask

Making a solution

Page 14: Uncertainties Salters A2 1. 2 Salters B There is guidance as to what the error is acknowledged to be if it is not stated on the apparatus It is generally

14

Example 1

250 cm3 of 0.2M iron (III) chloride solution250 cm3 of 0.2M iron (III) chloride solution

%037.0%100515.13

005.0% x

g

gU

MassMass

%080.0%100250

20.0%

3

3

xcm

cmU

Volume (volumetric flask)

Volume (volumetric flask)

%117.0%080.0%037.0% TUTotalTotal

Page 15: Uncertainties Salters A2 1. 2 Salters B There is guidance as to what the error is acknowledged to be if it is not stated on the apparatus It is generally

15

Example 2

250 cm3 of 0.2M HCl250 cm3 of 0.2M HCl

%7.0%1000.7

05.0%

1.2%

%5.0%1000.10

05.0%

3

3

3

3

xcm

cmU

xcm

cmUVolume

(10 cm3 measuring cylinder

Volume (10 cm3 measuring cylinder

%080.0%100250

20.0%

3

3

xcm

cmUVolume

(flask)Volume (flask)

%28.1%080.0%2.1% TUTotalTotal

Page 16: Uncertainties Salters A2 1. 2 Salters B There is guidance as to what the error is acknowledged to be if it is not stated on the apparatus It is generally

16

Comment:

The overall percentage uncertainty in measuring a volume of reagent for dilution is higher because three pieces of equipment were used (even if one was the same, it was used twice), and this piece of equipment had a lower precision than for the dilution of the solid reagent.

In general, the more equipment that is used, the greater the %U for that procedure.In general, the more equipment that is used, the greater the %U for that procedure.

Page 17: Uncertainties Salters A2 1. 2 Salters B There is guidance as to what the error is acknowledged to be if it is not stated on the apparatus It is generally

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For titration measurements, the uncertainty in each reading is:For titration measurements, the uncertainty in each reading is:

valuefinalin % valueinitialin % UU

The % U in the titre is:The % U in the titre is:

Titrations

100%x Value Effective

Precision21

Page 18: Uncertainties Salters A2 1. 2 Salters B There is guidance as to what the error is acknowledged to be if it is not stated on the apparatus It is generally

18

Comment:

Clearly, if the initial burette reading is 0.0 cm3, then it is unreasonable to include this in the calculation since it would return an infinite error.

To overcome this, use 2 x %U in final burette reading.

It is the same reasoning that tells you that the uncertainty in measuring a piece of paper with a mm-precision ruler is ± at either end, ie 2 x precision.

infinity0.0

05.03

3

cm

cm

Page 19: Uncertainties Salters A2 1. 2 Salters B There is guidance as to what the error is acknowledged to be if it is not stated on the apparatus It is generally

19

Comment:

The burette itself has an inherent error over the whole volume range (0.10cm3 for a 50 cm3 burette).

This could be included in the overall error by adding the %U due to this:

%100Titre

) Abs%

Ua10.00.50

)(

3

3

33

3

x) (cm

U (cmU

bsolutecmxcm

cmtitre

Page 20: Uncertainties Salters A2 1. 2 Salters B There is guidance as to what the error is acknowledged to be if it is not stated on the apparatus It is generally

20

Multiple additions

Multiple additions from a burette when it is not refilled can be treated as though the burette had been refilled.

Multiple additions from a burette when it is not refilled can be treated as though the burette had been refilled.

Adding to the reaction mixture from several burettes containing different substances:

%U from each burette must be calculated and the values added together

Adding to the reaction mixture from several burettes containing different substances:

%U from each burette must be calculated and the values added together

Page 21: Uncertainties Salters A2 1. 2 Salters B There is guidance as to what the error is acknowledged to be if it is not stated on the apparatus It is generally

21

Standard Curves

When creating a standard curve, the % U of each measurement and for the colorimeter must be added together to obtain the overall % U for the curve.

When creating a standard curve, the % U of each measurement and for the colorimeter must be added together to obtain the overall % U for the curve.

This may produce a high overall %U but remember, this is the MAXIMUM possible %UThis may produce a high overall %U but remember, this is the MAXIMUM possible %U

Page 22: Uncertainties Salters A2 1. 2 Salters B There is guidance as to what the error is acknowledged to be if it is not stated on the apparatus It is generally

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Example: Standard Curve

Salicylic acid/mol dm-3

Volume FeCl3/cm3

Volume Salicylic acid/cm3

Volume Water/cm3

0 10 0 100.004 10 2 80.008 10 4 60.012 10 6 40.016 10 8 20.020 10 10 0

Volumes added using 3 burettes. Salicylic acid dilutions used 50cm3 volumetric flasks and 1cm3 pipettesVolumes added using 3 burettes. Salicylic acid dilutions used 50cm3 volumetric flasks and 1cm3 pipettes

Page 23: Uncertainties Salters A2 1. 2 Salters B There is guidance as to what the error is acknowledged to be if it is not stated on the apparatus It is generally

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Uncertainty in standard curve

Dilution of salicylic acid: 50cm3 ± 0.12cm3 volumetric flaskDilution of salicylic acid: 50cm3 ± 0.12cm3 volumetric flask

%2.1%10050

12.0 5%

3

3

x

cm

cmxU

Transfer of salicylic acid: 1.0cm3 ± 0.012cm3 pipetteTransfer of salicylic acid: 1.0cm3 ± 0.012cm3 pipette

%6%1001

012.0 5%

3

3

x

cm

cmxU

Note, 5 volumes of 1cm3 were used in the whole curve

Page 24: Uncertainties Salters A2 1. 2 Salters B There is guidance as to what the error is acknowledged to be if it is not stated on the apparatus It is generally

24

Uncertainty in standard curve

INITIAL burette reading – salycilic acidINITIAL burette reading – salycilic acid

%7.5%1002

05.0%100

4

05.0

%1006

05.0%100

8

05.0%100

10

05.0%

3

3

3

3

3

3

3

3

3

3

xcm

cmx

cm

cm

xcm

cmx

cm

cmx

cm

cmU

FINAL burette reading – salycilic acidFINAL burette reading – salycilic acid

%7.5%1002

05.0%100

4

05.0

%1006

05.0%100

8

05.0%100

10

05.0%

3

3

3

3

3

3

3

3

3

3

xcm

cmx

cm

cm

xcm

cmx

cm

cmx

cm

cmU

Page 25: Uncertainties Salters A2 1. 2 Salters B There is guidance as to what the error is acknowledged to be if it is not stated on the apparatus It is generally

25

Uncertainty in standard curve

INITIAL burette reading – Iron (III) ChlorideINITIAL burette reading – Iron (III) Chloride

%3%10010

05.0 6%

3

3

x

cm

cmxU

FINAL burette reading –Iron (III) Chloride FINAL burette reading –Iron (III) Chloride

%3%10010

05.0 6%

3

3

x

cm

cmxU

Note, 6 volumes of 10cm3 were used

Page 26: Uncertainties Salters A2 1. 2 Salters B There is guidance as to what the error is acknowledged to be if it is not stated on the apparatus It is generally

26

Uncertainty in standard curve

INITIAL burette reading - waterINITIAL burette reading - water

%7.5%1002

05.0%100

4

05.0

%1006

05.0%100

8

05.0%100

10

05.0%

3

3

3

3

3

3

3

3

3

3

xcm

cmx

cm

cm

xcm

cmx

cm

cmx

cm

cmU

FINAL burette reading – waterFINAL burette reading – water

%7.5%1002

05.0%100

4

05.0

%1006

05.0%100

8

05.0%100

10

05.0%

3

3

3

3

3

3

3

3

3

3

xcm

cmx

cm

cm

xcm

cmx

cm

cmx

cm

cmU

Page 27: Uncertainties Salters A2 1. 2 Salters B There is guidance as to what the error is acknowledged to be if it is not stated on the apparatus It is generally

27

Uncertainty in standard curve

ColorimeterColorimeter

%33%10063.0

005.0%100

52.0

005.0%100

37.0

005.0

%10026.0

005.0%100

16.0

005.0%100

02.0

005.0%

xxx

xxxU

Total % Uncertainty = (1.2 + 6+ 3+3+5.7+5.7+5.7+5.7+33)%

= 69% (2sf is enough)

Page 28: Uncertainties Salters A2 1. 2 Salters B There is guidance as to what the error is acknowledged to be if it is not stated on the apparatus It is generally

28

Example 2: Gas Syringe

Precision of gas syringe – 1cm3.Precision of gas syringe – 1cm3.

100%x Value Effective

Precision%

21

U

Find the uncertainties for all other measurements, eg balance, making solutions and the measurement of your independent variable (e.g.time) add to the %U of the gas syringe.

Find the uncertainties for all other measurements, eg balance, making solutions and the measurement of your independent variable (e.g.time) add to the %U of the gas syringe.

For the single curve resulting from one value of your variable, add together all of your %U to give you the overall %U for that experiment.

For the single curve resulting from one value of your variable, add together all of your %U to give you the overall %U for that experiment.

Page 29: Uncertainties Salters A2 1. 2 Salters B There is guidance as to what the error is acknowledged to be if it is not stated on the apparatus It is generally

29

Example 2: Gas Syringe

%33%10063.0

005.0%100

52.0

005.0%100

37.0

005.0

%10026.0

005.0%100

16.0

005.0%100

02.0

005.0%

xxx

xxxU

If a gas syringe method is used to measure a rate of reaction at different substrate concentrations or other condition, then the error for your reaction rate curve should, theoretically be the sum of all %U from the individual curves from which the initial rate (gradient) was taken.

The %U from the smallest values, closest to the origin, are likely to be the highest, and so it is not unreasonable to add together the largest individual uncertainties from each individual curve in order to approximate an overall maxiumum %U in the derived reaction rate curve if that is your intent.

However, this calculation is not really necessary of you are looking for the order of a reaction, since the shape of the resulting curve is all you need.

Page 30: Uncertainties Salters A2 1. 2 Salters B There is guidance as to what the error is acknowledged to be if it is not stated on the apparatus It is generally

Improvements to technique

30

Page 31: Uncertainties Salters A2 1. 2 Salters B There is guidance as to what the error is acknowledged to be if it is not stated on the apparatus It is generally

31

http://www.titrations.info/pipette-burette

The bottom of the concave meniscus must be precisely on a calibration mark. To make reading of the meniscus position easier we can use piece of paper with a horizontal black stripe, about an inch and half wide.

If the paper is held half an inch behind a burette with the stripe about a half an inch below the meniscus, the solution surface seems to be black and is much easier to see.

Precision for burettes and graduated pipettes