CHEM2241 Analytical Chemistry I Mid-term summary

Question settings – Error Propagation

1) Error propagation & Number of digits in operations
1. Number of digits 2.

Determined by
decimal places

Determined by
Significant figures

e.g. pH = - log [H+]

[H+] = 3.75 × 10-5
pH = 4.426
3 s.f.
3 d.p.

• Discuss whether error is significant: compare relative errors

2) Types of error
Systematic error Random error
• Related to experimental design • Related to experimenter
e.g. instrument error, method error
• Instrument errors: fixed by calibration • Cannot be fixed
• Method errors: fixed by independent analysis,
blank determination, variation in sample size,
using Standard Reference Material (SRM)
• Affect accuracy • Affect precision & accuracy

3) Concentration – unit conversion (g/L, M, ppm, ppb)

• 1 ppm = 1 𝜇g/g
• 1 ppb = 1 𝜇g/kg

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 Question settings – Buoyancy correction
Buoyancy effect of air in pipet calibration
• It is due to an object immersed in a gas/liquid is buoyed up by a force equal to the weight
of fluid displaced.
• The apparent weight of an object weighed in air is less than its true weight by the weight
of displaced air.

Buoyancy correction Correction factor

𝜌%(" 𝜌%("
𝑀!"#$ = 𝑀%&&%"$'! × (1 + − )
𝜌)*+$,! 𝜌-!$$.

• 𝜌)*+$,! may change due to thermal expansion

• In calibration of pipet, low-density liquid is not preferred because the relative error in
weighing is larger. It is not because of buoyancy error since it is not large and can be
corrected.

Common errors in pipet calibration

1. NOT using paper strip to hold weighing flask
2. NOT holding pipet above the graduated mark
3. NOT drying ground glass joint
4. NOT using lower meniscus
5. NOT resting pipet tip on the beaker wall when adjusting liquid level
6. NOT waiting for 10 secs before drawing out the final drop of liquid
7. NOT touching pipet tip against wall of flask bottom perpendicularly
8. Wiping exterior pipet tip with tissue before adjusting liquid level

Check if analytical balance is ready to use

• If air bubble is located inside the red bubble, it is ready to use
• If not, adjust the two level screws at the front: (1) screw for one – horizontal movement;
(2) screw for both – vertical movement

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 Question settings – Sample Preparation
An ultrapure compound that
1. Characteristics of a primary standard serves as the reference material
• High purity (established methods for validation) for quantitative analysis
• Absence of hydrate water
• Atmospheric stability (stable when dried by heat or vacuum)
• Reasonable solubility in the titration medium
• Reasonably large molar weight
• Modest cost

2. Experimental procedures
e.g. Preparing standard solution by dissolving solid
Describe the preparation of 100.0 mL of standard solution of K from KCl. [MW: K = 39.0983,
Cl = 35.453.]

Suggested answer
• 1 ppm = 1 𝜇g/g ≅ 1𝜇g/mL for diluted aqueous solution.
• Calculate mass of KCl required (=1.9068 × 10-3 g KCl/mL, i.e. 0.19 g KCl/100 mL)
• Weigh approximately 0.19 g accurately
• Dissolve it in deionized water in a beaker
• Transfer the solution to a 100-mL V-flask and dilute to the mark, make 10× dilution
twice (10-mL pipet & 100-mL V-flask)

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 3. Decomposition and dissolution

Heating with aqueous strong acids in open

Microwave digestion
vessels
• Wet ashing
• Wet ashing - oxidative decomposition of organic
Principle • Microwave energy is transferred directly to all molecules of the
samples by liquid oxidizing reagents
solution nearly simultaneously without heating the vessel.
• Weigh sample into a conical flask and add acids • Weigh sample into a Teflon vessel and add oxidizing acids
Procedures • Swirl when heating until dissolve. Cool briefly. • Seal the vessel using correct torque, digest for 5-10 minutes.
• Cool, remove cap and dilute with deionized water
• Incomplete dissolution of analyte
Sources of
• Loss of volatile analyte (e.g. As, B, Cr, Hg, Sb, Se, Sn are lost at relatively mild temp.)
errors
• Contamination
Contamination supplementary Why microwave digestion over open-vessel heating ?
• Impurities from analyte species (Even at small • Faster rate due to higher temp. (higher than b.p., temp. in open-
concentration may lead to significant error) vessel heating) inside sealed container
Remarks • Reaction of solvent with digestion vessel • Eliminating losses of volatile analytes
• Decrease in blank values (less contamination from lab
• Need more reagent for digestion due to environment & using smaller quantity of reagent)
evaporative loss

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 High-temperature ignition in air / oxygen Fusion in molten salt media
Dry ashing - oxidation of organic sample with oxygen or • Decomposing inorganic materials by Fluxes
Principle air at high temperature, leaving inorganic component • Mix inorganic samples with flux, heat in heavy-duty oven
for analysis (~1000ºC)
/ Common practice
• Use liquid reagent first, undecomposed residue is isolated
Procedures by filtration and fused with suitable flux.
• After cooling, the melt is dissolved and combined with the
major portion of sample.
Sources of Same • Volatilization loss
errors • Possible contamination by impurities in fluxes
• High salt content, causing difficulties in subsequent steps
of analysis
Remarks • Lower recovery compared to wet ashing (volatile /
components escape)
• Incomplete combustion with pyrolytic organic
materials

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 Question settings – Microwave Digestion

How microwave digestion reduces errors

1. evaporative loss ↓ → use less reagent → interference by reagent contamination ↓
(decrease blank values)
2. volatilization loss of analytes ↓

The function of digestion reagents

Reagents Functions & Remarks
① Attack most metals, but not noble metals
1. HNO3
② Destroy organic materials
① Attack some iron-alloys & stainless steel
2. HClO4 ② Explosive when in contact with org. & easily oxidized inrog.
Materials è use with HNO3
3. HCl ① Better solvent than oxidizing acids, in particular for oxides
① Suppress passivation (formation of protective oxide layer) of
4. HF
metal surface
① Increase solvent action
5. H2O2 / Br2
② Hasten oxidation of organic materials
① 3 volumes of HCl & 1 volume of HNO3
6. Aqua Regia ② Fresh batches always prepared when required
③ Dissolves noble metals & suflides

Safety issues & Precautions

Type Safety issues & Precautions
① may spark when subjected to microwave radiation
1. Metallurgical ② react with acids to give H2 è use open/purge container with
N2 to remove oxygen
2. Metals ① become so hot that Teflon is melt è use silica container
① form explosive mixtures with oxygen
3. Organic ② digestion gives CO2 è venting of gas may cause loss of
small droplets
① They have high b.p. è use quartz / borosilicate container
4. H2SO4 / H3PO4
(but will be attacked by HF)

Function of safety membrane

• In case of bursting, safety membrane is rupturable for relieving pressure

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 Question settings - Statistical Tests

There must be parts involving the use of Q-test, F-test & Student’s t-test.

1) Definition of CI & CL. Why is the 99% CI wider than the 95% CI?
• Confidence level refers to the probability that the true mean lies within a certain
interval and is often expressed as a percentage.

• Confidence interval for the mean is the range of values within which the pop. mean 𝜇 is
expected to lie with a certain probability

• If we repeated sets of measurements many times, there is 99% chance that true value
lies in the 99% CI, which must be greater than, similarly 95% chance that true value lies
in the 95% CI.

2) List three difference cases for comparison of the means with Student’s t, and write
the equations used in the each of the cases.

3) The pooled S.D. is a better estimate of the population S.D. than the S.D. of individual
data sets. Explain this.

Answer
Pooling involves a larger no. of measurements can reflect variations that arise due to
sampling.

If s is not good
Establishing Confidence limits estimate, use t form

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 Hypothesis testing
1.1 z-test
|𝒙
0 − 𝝁|
𝒛𝒐𝒃𝒔 = √𝑵
𝝈

If 𝑧)*- > 𝑧,"(!(,%. , then null hypothesis 𝐻2 (no difference) is rejected

If s is not good estimate of 𝝈, this implies that the given data is not a perfect Gaussian
distribution. t-test is used instead of z-test.

1.2 Student t-test

Type Remarks Formula(e)

• Compare measured result |𝑥̅ − 𝜇|
1. Small sample t-test 𝑡)*- = √𝑁
with authentic value 𝑠

most common • Compare mean of two |𝑥̅3 − 𝑥̅4 | 𝑁3 𝑁4

in exam 𝑡)*- = >
sets of measurements 𝑠&)).$5 𝑁3 + 𝑁4
2. The t-test for [Do the data indicate a 𝑠&)).$5
differences in means diff. between two
(𝑁3 − 1)𝑠34 + (𝑁4 − 1)𝑠44
measurements?] =>
𝑁!)!%. − 2
• D.F. = 𝑁!)!%. – 2

@𝑑̅ @
Two methods, diff. samples: 𝑡)*- = √𝑁
𝑠5
3. Paired t-test diff. due to samples
themselves ∑(𝑑( − 𝑑)4
𝑠5 = >
𝑁−1

If 𝑡)*- > 𝑡,"(!(,%. , then null hypothesis (no difference) is rejected

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2. Q-test - Discarding outliners

Null hypothesis: outliner is retained

If 𝑄)*- > 𝑄,"(!(,%. at a particular confidence level, then null hypothesis is rejected.
(discarded)

Steps
1. Sort data in order
2. Find the largest gap thus the outlying data

3. F-test - Comparison of Variances

𝑠34
𝐹)*- = 4
𝑠4
Null hypothesis: there is a difference between precision of two methods
If 𝐹)*- > 𝐹,"(!(,%. at a particular confidence level, then null hypothesis is rejected.

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 Question settings – Least Squares & Calibration Curve
Absorbance
𝑦(±Δ𝑦) − 𝑏(±Δ𝑏) 𝑦 = 𝑚𝑥 + 𝑏
𝑥(±Δ𝑥) = 𝑅4 = 0.99 …
𝑚(±Δ𝑚)

Absorbance
Concentration
Conc.

Type 1: Error Propagation

𝑠3 = J𝑠64 + 𝑠*4
If 𝑠6 given 𝑠3
𝑟𝑠𝑑3 = ( )
If 𝑠6 is not given, 𝑦−𝑏
ignore 𝑠6 Δ𝑚
𝑟𝑠𝑑4 = ( )
𝑚
𝑠7 = J𝑟𝑠𝑑34 + 𝑟𝑠𝑑44

Type 2: Using Calibration results

Uncertainty in 𝑦 Given absorbance

Uncertainty in 𝑥
Mean absorbance

Total # of data pt.

Only one value : M = 1
Mean: M = # of measurements

(A) What is given ?

• Slope 𝑚 & uncertainty 𝑆8 ; y-intercept 𝑏 and uncertainty intercept 𝑆* ; 𝑅4
• # of data points 𝑛 (conc. and corresponding absorbance)
• Average conc. & average absorbance 𝑦O Find 𝑺 !!!𝒙𝒙

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• Type 1: Given Uncertainty regression 𝑆" • 𝑆77 = T9 ! U
"

• Type 2: Not given 𝑆" , we apply error propagation to estimate.

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(B) Question analysis
Type 1 (Given 𝑺𝒓 )
What is the concentration ? Express your results in molar / ppm along with its uncertainty at
the 95% CL.

1. Find concentration - substitution 2. Find 𝑆,

𝑦 = 𝑚𝑥 + 𝑐

3. Find confident interval

𝐶. 𝐼. = 𝑥 ± 𝑡'<4 × 𝑆,

Type 2 (Not given 𝑺𝒓 )

e.g. Determine the concentration and estimate its uncertainty.
• Substitute numbers into 𝑦 = 𝑚𝑥 + 𝑐 to find concentration
• Use error propagation to estimate the uncertainty.

(C) Discussion
1. Discuss possible sources of errors.
• Fingerprint attached on the sample cell.
• Bubbles present in sample solution. This increases the reflection of electromagnetic
wave (UV-Vis).

2. Why is it most accurate to measure the absorbance in a range of 0.4 to 0.9 ?

• At low A values, there is only little difference between incident & transmitted power
• At very high values of A, transmitted power is small and is subjected to larger %ER.

3. Method to reduce measurement errors

• Measure the reagent blank and make blank correction.

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