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CLASSICAL ANALYSIS

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DEFINITIONS
o Absolute error – The numerical difference between measured and true values.
o Accuracy – Closeness of a result to the accepted or true value.
o Accuracy – How close a measured value is to the true value.
o Accuracy – The closeness of a measurement to the true or accepted value.
o Analyte – The substance being measured or analyzed in a sample.
o Blank – A sample that contains all components except the analyte.
o Buffer – A solution that resists changes in pH upon addition of acid or base.
o Contaminant – An undesired substance present in a sample.
o Contamination – Introduction of foreign or impure substances into a sample.
o Contamination – The introduction of impurities into a sample.
o Distribution coefficient – Ratio of a compound’s concentration in two immiscible solvents.
o End point – A detectable change signaling the end of a titration.
o End point – A physical change indicating titration completion.
o Equivalence point – The point in a titration where reactants are in exact stoichiometric ratio.
o Equivalence point – The point where equal molar amounts of reactants have reacted.
o Interference – A substance that alters or masks analytical results.
o Interference – Effects from other substances that distort analytical measurement.
o Nucleation – The initial process where particles start to cluster to form a new phase.
o Occlusion – The entrapment of impurities within a crystal during formation.
o Outlier – A data point that significantly deviates from the rest.
o Outlier – A result that deviates markedly from the rest of the data set.
o Precision – Closeness among a series of repeated results.
o Precision – The consistency or repeatability of measurements.
o Precision – The degree to which repeated measurements agree with each other.
o Qualitative analysis – Identification of which substances are present.
o Quantitative analysis – Measurement of how much of a substance is present.
o Random error – Unpredictable variations in measurement results.
o Random sampling – A sampling technique where each item has equal chance of selection.
o Random sampling – Selection where every individual has an equal chance.
o Relative error – The absolute error expressed as a fraction or percentage.
o Repeatability – Ability to get same results under identical conditions by same analyst.
o Repeatability – The closeness of results under identical conditions.
o Reproducibility – Ability to get consistent results under different conditions or analysts.
o Reproducibility – The ability to obtain similar results under varied conditions.
o Standard solution – A solution of known and precise concentration.
o Statistical sampling – Selection method using probability theory to represent a population.
o Statistical sampling – Use of probability and statistics to choose representative samples.
o Systematic error – Consistent error due to flaws in procedure or equipment.
o True value – The actual or theoretically correct value of a measurement.
o True value – The correct or accepted value of a quantity.
o Trace Analysis: Trace analysis refers to the measurement and analysis of very low concentrations
(usually parts per million or parts per billion) of a substance within a sample.
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SUMMARY NOTES
Advantages and Disadvantages of Instrumental Methods of Analysis
Advantages Disadvantages
High sensitivity and precision High initial cost of instruments
Ability to analyze small sample sizes Requires skilled operators
Faster analysis with automated processes Maintenance and calibration are expensive
Provides detailed and accurate results Limited to specific types of analysis
Suitable for complex samples and mixtures Potential interference from other substances
Can perform continuous monitoring May require specialized software or expertise
Characteristics of a Primary Standard:
• High purity
• Stable in air (non-hygroscopic)
• High molar mass
• Readily and completely soluble in water
• Reacts stoichiometrically (one clear reaction)
• Not affected by light or environmental conditions
• Easily weighed and handled
• Inexpensive and readily available
Challenges Associated with Trace Analysis
1. Contamination: Due to the low concentration of analytes, even small amounts of
contamination from the environment or equipment can significantly affect results.
2. Interference: Other substances present in the sample may interfere with the detection or
measurement of the target analyte, leading to inaccurate results.
Standard Solution and Primary Standard
• Standard Solution: A solution of known concentration used for titrations and calibration of
instruments.
• Primary Standard: A highly pure substance used to prepare standard solutions.
o Requirements:
1. Must be pure and stable.
2. Should have a known and consistent reactivity.
Three Ways to Minimize Errors in Volumetric Analysis
• Use calibrated and clean glassware
• Perform titrations at eye level to avoid parallax error
• Avoid endpoint overshooting; add titrant dropwise near endpoint
Blank Analysis
A blank analysis involves running the same procedure without the analyte to detect contamination.
Usage in trace analysis:
• Helps identify and correct for impurities in reagents or environment
• Its results are subtracted from sample readings to get true values
• Ensures accuracy in low-concentration measurements
Clearly distinguish between the following terms: i) Contamination vs. Interference ii) Qualitative vs.
Quantitative analysis
i) Contamination vs. Interference
• Contamination: Unintended introduction of foreign substances that alter sample
composition (e.g., dirty glassware).
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• Interference: A substance in the sample that affects the measurement process by reacting
with or masking the analyte (e.g., overlapping absorbance).
ii) Qualitative vs. Quantitative Analysis
• Qualitative: Identifies the presence or type of substance.
e.g., Flame test showing presence of sodium
• Quantitative: Measures how much of a substance is present.
e.g., Titration determining molarity of acid
Distinguish between accuracy and precision.
Accuracy: Closeness of a measurement to the true or accepted value.
Precision: Closeness of repeated measurements to each other.
When selecting the most appropriate analytical method for chemical analysis, consider the following three
factors:
o Sensitivity: The method should be able to detect and quantify the target analyte at the required
concentrations.
o Accuracy and Precision: The method should provide reliable and reproducible results. It should
give accurate (close to the true value) and precise (consistent results across multiple trials)
measurements.
o Interference and Selectivity: The method should be able to differentiate the target analyte from
other substances that may be present in the sample.
Describe three major steps in the qualitative analysis of sulfur in fuels.
Sample Preparation: The fuel sample is prepared by combustion or other methods to release sulfur
compounds as gases.
Sulfur Detection: A chemical reagent or detector is used to react with sulfur compounds (e.g., using
lead acetate paper for detecting hydrogen sulfide).
Confirmation: The presence of sulfur is confirmed by observing color changes or by comparing
results with known standards.

Differentiate between random sampling and statistical sampling.

Random Sampling: Every member of the population has an equal chance of being selected,
ensuring a fair representation.
Statistical Sampling: A broader method where a sample is selected based on specific statistical
techniques to represent the population and ensure valid conclusions.
Define trace analysis and outline two challenges encountered by this type of analysis.
• Definition of Trace Analysis: Trace analysis refers to the measurement of very small
quantities of a substance (usually in the ppm or ppb range).
• Challenges:
1. Contamination: It is difficult to avoid contamination when working with such low
concentrations.
2. Sensitivity: The methods used must be sensitive enough to detect minute amounts of
the substance accurately.
Briefly describe three steps involved in a typical gravimetric analysis.
• Precipitation: The analyte is precipitated by adding a reagent to the solution.
• Filtration: The precipitate is separated from the solution by filtration.
• Drying and Weighing: The precipitate is dried and weighed to determine the amount of
the analyte in the sample.
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ANALYSIS
Using the 95% confidence level, determine if 27.0% in the following %Fe data set should be rejected: 29.3, 30.8, 31.1, 30.4, 27.0

A 0.1 M solution of HCl was used to titrate 10.00 mL of 0.1 M NaOH. The following titration volumes (in mL) of acid were
recorded: 9.88, 10.18, 10.23, 10.39, 10.35: Calculate the 95% confidence limits of the mean volume.
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A 0.470 g sample containing sodium carbonate (Na₂CO₃) was reacted with 50.00 mL of 0.1 M HCl. The excess acid was back-
titrated with 20.00 mL of standardized 0.1 M NaOH. Calculate the percentage of sodium carbonate in the sample. (Molar mass
of Na₂CO₃ = 105.99 g/mol)

In an experiment to determine the Chemical Oxygen Demand (COD) of an effluent, the following values (in mg/kg) were
recorded: 4.35, 4.27, 4.38, 4.31, and 4.27.
Calculate: i) Mean ii) Standard deviation iii) Relative average deviation
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In an experiment to determine calcium content in honey samples, the following replicate values were
obtained (in ppm): 4.14, 4.82, 6.88, 4.12, and 4.45. Determine whether the value 3.88 ppm is an outlier
using: i) 3d test ii) 4d test

Describe clearly how to prepare the following acid solutions: i) 600 mL of 0.4 M H₂SO₄ (Sulphuric acid) — given
density = 1.84 g/cm³ and purity = 98% ii) 800 mL of 0.2 M HCl (Hydrochloric acid) — given density = 1.16 g/cm³
and purity = 37%
(Atomic masses: H = 1.007, S = 32.010, O = 15.999, Cl = 35.456)
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a) The lead content in petrol was analyzed using two methods (ppm). Use a paired t-test at 95%
confidence level to determine whether the methods differ significantly.
Old method: 10.2, 12.7, 8.6, 17.5, 11.2, 11.5
Standard method: 10.5, 11.9, 8.7, 16.9, 10.9, 11.1
b) Calculate the pH and pOH of a 0.004 M acetic acid solution. (Ka = 1.76 × 10⁻⁵)
c) State three ways to minimize errors in volumetric analysis.
d) What is meant by blank analysis? How is it used to reduce contamination in trace analysis?

a) Using statistical parameters such as range, mean, and standard deviation, assess the accuracy and
precision of the following results (in ppm) for four samples A–D. The true value is 42.0 ppm.
Comment on the presence of random and systematic errors.
Sample Results (ppm)
A 39.8, 43.6, 42.1, 40.1, 43.5
B 43.5, 42.7, 43.8, 43.1, 42.7
C 42.2, 41.6, 42.1, 41.8, 42.5
D 42.5, 41.6, 42.1, 41.9, 41.1
We'll compute the Mean, Standard Deviation (SD), and Range for each sample, then interpret
accuracy and precision.
Sample Mean (ppm) SD Range Accuracy (from 42.0) Precision Errors
A 41.82 1.51 3.8 High accuracy Low Random
B 43.16 0.45 1.1 Low (Systematic bias) High Systematic
C 42.04 0.32 0.9 Very high Very High None
D 41.84 0.50 1.4 High High Slight random
Interpretation:
• Sample C is most accurate and precise — closest to true value with lowest SD.
• Sample B is precise (low SD) but not accurate — likely systematic error.
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• Sample A is least precise — high SD, wider range; shows random error.
• Sample D is fairly accurate and precise.
The following cadmium (Cd) replicate measurements were obtained in ppm: 0.4026, 0.4029, 0.4023,
0.4031, 0.4025, 0.4032, 0.4027, and 0.4026…Assuming no determinate error, calculate the 95%
confidence interval for the true mean.

During the determination of calcium content in fermented milk, the following replicate
measurements (in ppm) were recorded:
0.12, 0.14, 0.13, 0.17, 0.13, 0.14, 0.15
Calculate the following:
i) The range of the results (2 marks)
ii) The mean calcium concentration (2 marks)
iii) The standard deviation of the data set (3 marks)
iv) The relative average deviation (2 marks)
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The analysis of potassium in egg shells yielded the following results (μg/L):
6.00, 6.23, 5.95, 6.08, and 15.04 μg/L. Using the Q-test at a 90% confidence level, determine whether the value 6.23 μg/L should
be rejected or retained.

A 10.0 mL sample of potassium iodide (KI) was analyzed by adding an excess of silver nitrate solution to produce silver
iodide (AgI) crystals, which were filtered from the solution. The reaction is:

Given:
Mass of silver iodide (AgI) = 2.183 g
Molar mass of AgI = 143.88 g/mol:
What is the molarity of the original KI solution?
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A student placed 0.125 g of chalk sample in a 250 mL flask and added 50.0 mL of 0.20 M HCl using a pipette. The
excess HCl was then titrated with 0.25 M NaOH. 32.12 mL NaOH was required to react completely with the excess
HCl. Calculate the mass of calcium carbonate (CaCO₃) present in the chalk sample. (Ca = 40.078, O = 15.999, C =
12.000)

During an analysis to determine the fluoride content in Dasani bottled mineral water, the following
replicate results were obtained: 1.98, 2.02, 1.86, 1.97 mg/L. Determine whether 1.86 mg/L is suspect
using: i) 4D test ii) 3S test (3 Marks each)
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A new method for the determination of the chemical oxygen demand (COD) of wastewater was compared with the
standard method. The following results were obtained for a sewage effluent sample:
Mean (mg/L): Standard method: 72, New method: 72
Standard deviation (mg/L): Standard method: 3.31, New method: 1.51
For each method, six determinations were made. Is the precision of the new method significantly greater than that of
the standard method at a 95% confidence level? (4 Marks)

A 0.25g sample of silver plate was dissolved in nitric acid and gravimetrically analyzed by adding an excess of sodium
chloride solution. The silver chloride precipitate was digested for 15 minutes at 95°C and filtered. The mass of the
collected silver chloride was 0.1784g. Calculate the percentage by weight of silver in the plate. (3 Marks)
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ii) Using statistical measurements (mean, range, and standard deviation), comment on the
accuracy and precision of the following sets of results (g/kg) in terms of random and
systematic errors. The true value is 42.0 g/kg. (4 Marks)
Method A: 43.5, 42.7, 43.8, 43.1, 42.7
Method B: 42.2, 41.6, 42.1, 41.8, 42.5
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a) i) Explain the term buffer (2 Marks)

ii) Calculate the pH of a buffer prepared by mixing 0.250 mol of acetic acid with 0.10 mol of sodium
acetate and diluting to 1.001 L (4 Marks)

A chemist carried out an analysis to determine the percentage of calcium in unknown rock using two
methods, a standard method and a new method. The replicate determinations of calcium were as follows:
Standard method: 10.5, 11.9, 8.6, 16.9, 10.9, 11.1
New method: 10.2, 12.7, 8.5, 17.5, 11.2, 11.5
i) Calculate the mean and the standard deviation of the two methods (4 Marks)
ii) Use paired t-test to determine if the two methods differ significantly at 95% confidence level (4 Marks)
iii) State and explain two advantages of classical methods of analysis (3 Marks)

Paired t-test to Determine if the Methods Differ Significantly

• Null Hypothesis (H₀): There is no significant difference between the two methods.
• Alternative Hypothesis (H₁): There is a significant difference between the two methods.
Using the paired t-test formula for differences, calculate the t-value and compare it with the critical t-value at 95%
confidence. If t > t₀.₉₅, reject the null hypothesis.
Advantages of Classical Methods of Analysis
1. High accuracy: Classical methods, such as titrations, are often very precise and accurate.
2. Low cost: They typically require less expensive equipment compared to instrumental methods.
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c) Calculate the 95% confidence interval and confidence limits for the following data: 10.2, 9.7, 9.9, 9.8,
10.1, and 10.6 ppm (3 Marks)
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The mercury content of a fish sample was analyzed by two methods (mg/kg) as follows:
New Method: 2.06, 1.93, 2.12, 2.16, 1.89, 1.95
Standard Method: 2.35, 2.44, 2.70, 2.48, 2.44
Using the Student’s t-test at a 95% confidence level, determine if the means of the two methods
differ significantly.
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The following replicate measurements of cadmium content in soil samples were obtained during
analysis:
0.4026, 0.4029, 0.4023, 0.4031, 0.4025, 0.4032, 0.4027, and 0.4026 ppm.
Assuming no determinate errors, within what range are you at the 95% confidence level that the true mean value of
the cadmium content falls?

A 0.600g sample of K₂CO₃ (138.2055 g/mol) is dissolved in enough water to make 200 mL of solution A. A 20.0
mL aliquot of solution A is taken and put into a conical flask, and 20.0 mL of 0.17M HCl is added. The resulting
solution is then titrated with 0.1048 M NaOH solution.
Calculate the volume of NaOH used in the titration.
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Calculate the pH and pOH of a 4.0 x 10⁻² M solution of ethanoic acid, given that its
Ka = 1.82×10−4
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Describe how the following solutions are prepared in the laboratory, showing all your workings:
i) 500 mL of 0.6 M hydrochloric acid (Density of HCl = 1.18 g/cm³, H = 1.007, Cl = 35.456, %
purity = 37%).
ii) 400 mL of 0.5 M sodium carbonate (Na₂CO₃).
iii) 500 mL of 2.0 M nitric acid (N = 15.00, O = 15.999, density = 1.51 g/cm³, % purity = 63%).
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Using mean, range, and standard deviation, comment on the accuracy and precision of the
following sets of results (ppm) in terms of random and systematic errors. The true value is 42.0
g/L.
• A: 39.8, 43.6, 42.1, 40.1, 43.5
• B: 43.5, 42.7, 43.8, 43.1, 42.7
• C: 42.2, 41.6, 42.1, 41.8, 42.5
• D: 42.5, 41.6, 42.1, 41.9, 41.1
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A new method for determining the chemical oxygen demand of wastewater was compared with the
reference method. The following results were obtained for a sewage effluent sample:
• New method mean: 19.65 mg/L, Standard deviation: 0.673, Sample size: 6
• Reference method mean: 19.24 mg/L, Standard deviation: 0.324, Sample size: 5
Is the precision of the new method significantly greater than that of the reference method at
the 95% confidence level? (4 Marks)
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