Dr. MOLEFE D.

ROOM 311 NSB

dan.molefe@smu.ac.za

Analytical Chemistry 2
(MCHA022)

2023
Lecture Times

Wednesday: 9.15 -10.40

NSB 015
Thursday: 9.15 -10.40
NSB 015
Friday: 8.30 – 9.10
NSB 015
 Academic Conduct

• Science is a profession, and ethical behaviour is expected of professionals.

• Thus, in Analytical Chemistry 022 course, you are expected to act in a

professional manner.

• Academic dishonesty is defined in the Regulations Handbook and will be dealt

with according to the guidelines therein.
 ……
• Exchanging information on assignments or exams where such an
exchange has been forbidden and plagiarism are violations of the
standards set forth in this course and the Regulations book in general.

• Appropriate penalties will be imposed, which could include referral to

the HOD/Dean`s office and finally exclusion from the course.
 ……
• Class Notes: Notes for the topics will be available on Blackboard.
Please Print and Bring the notes to class!!!

• Attendance: You are expected to attend every class and laboratory session.

• If you miss an assignment or examination, contact me to schedule a makeup.

If you know you will miss any course activity, speak to me in advance.
 What is Analytical Chemistry?
What chemical species are present in a sample?
How much of each chemical species is present?
AC: The area of chemistry responsible for characterizing the composition
of matter, both qualitatively (Is there..) and quantitatively (How much..).
NB!!! Most chemists regularly make qualitative and quantitative
measurements

Important Areas:
(a) Quality control in the process industries
(b) Environmental analysis
(c) Clinical and biological studies
(d) Fundamental and applied research
 2 main areas of Statistics

Statistics is a branch of science dealing with collecting, organizing,

summarizing, analysing and making decisions from the data
• Descriptive: focus on methods for collecting, organizing, and describing data
• Inferential: deals with methods that use sample results, to help in estimation or
make decisions about the population.
 How to determine the CL Intervals

In replica analysis done by 4 MSc. Analytical Chemistry students from UP, the
carbohydrate content of a glycoprotein is found to be
12.6 11.9 13.0 12.7 and lastly 12.5g of carbohydrate per 100g of protein.
Help them to find the 50 and 90% confidence interval for the carbohydrate
content.
Mean: sum up all the numbers, then divide by how many numbers there are.

Median: the middle value in a set of data that has been arranged in increasing or
decreasing order
Example: 20.12, 19.67, 19.82, 20.21, 19.91, 20.01, 19.73 (N = 7)
median = 19.91
For an even number of measurements, the median is the average of the central
pair
Example: 20.12, 19.67, 19.82, 20.21, 19.91, 20.01 (N = 6)
median = 19.96
Range for a data set is depends on two values (the smallest and the largest
values)
Range = Largest value – Smallest value
Midrange: is defined as the sum of the lowest and highest values in the data set
divided by 2
Mode: the value/values in the data set that occur most frequently.

Variance (s2)
 Standard Deviation, s
A valuable parameter expressed by:

,xi is a measured result, μ is the true mean and N is the number of results in the set.
NB!!! Unfortunately, μ is never known and the mean derived from the set of results
has to be used. In these circumstances the degrees of freedom are reduced by one
and an estimate of the true standard deviation is calculated from:

Degree of Freedom
The number of degrees of freedom possessed by a replicate set of results equals the total
number of results in the set. When another quantity such as the mean is derived from the set, the
degrees of freedom are reduced by one, and by one again for each subsequent derivation made.
where M = N1 + N2 + . . . NK. One degree of freedom is lost with each set pooled.

Pooled standard deviation

√ s12 (n1-1) + s22 (n2-1)/(n1+ n2-2)
n1, n2: Sample size for group 1 and group 2, respectively.
s1, s2: Standard deviation for group 1 and group 2, respectively.

t = ⴟ1 - ⴟ2 – 0/sp√1/n1 + 1/n2

If t exp is less t critic at the degree of freedom (n1+ n2 -2) at a CI, then Reject the null hypothesis
 Exercise

Sample 1: 6, 6, 7, 8, 8, 10, 11, 13, 15, 15, 16, 17, 19, 19, 21
Sample 2: 10, 11, 13, 13, 15, 17, 17, 19, 20, 22, 24, 25, 27, 29, 29
Calculate the pooled standard deviation between these two
samples
Answ:5.789564
 Comparing tutorials classes at SMU
In a University, a tutorial class accommodates a certain number of students. It is
supposed that a new to be build tutorial class will accommodate more on the
average than the used. To test that hypothesis, the spaces it takes each class to
pack ten students are recorded below. The results, in cm, are shown in the tables.
New class
42.1 41.3 42.4 43.2 41.8 41.0 41.8 42.8 42.3 42.7
Old class
42.7 43.8 42.5 43.1 44.0 43.6 43.3 43.5 41.7 44.1

Do the data provide sufficient evidence to conclude that, on the average, the
new class packs more students? Perform the required hypothesis test at the
5% level of significance using the rejection region approach
 Exercise

A study is being performed by Chemistry department from SMU for Lancet

laboratories to see if there is a correlation between the concentration of
chromium in the blood and suspected disease. Blood samples from a series of
volunteers with a history of disease and other indicators of susceptibility
analysed and compared with the results from the analysis of samples from
healthy control subjects. From the following results, calculate the standard
deviation.
Control group (ppb Cr): 18 23 12 18 9 28 11 10
Disease group: 15 25 15 17 10 32 9 8
 The limits of confidence interval are given by
Values of t for various levels of probability

Confidence level (%)

Degrees of freedom 50 80 90 95 99 99.9

1 1.00 3.08 6.31 12.7 63.7 637
2 0.82 1.89 2.92 4.30 9.92 31.6
3 0.77 1.64 2.35 3.18 5.84 12.9
4 0.74 1.53 2.13 2.78 4.60 8.60
5 0.73 1.48 2.02 2.57 4.03 6.86
6 0.72 1.44 1.94 2.45 3.71 5.96
7 0.71 1.42 1.90 2.36 3.50 5.40
Once the reliability of a replicate set of measurements has been established
the mean of the set may be computed as a measure of the true mean.
 Example

If the analysis of a sample for iron content yields a mean result of 35.40% with
a standard deviation of 0.30%, the size of the confidence interval will vary
inversely with the number of measurements made.
For two measurements, the confidence interval (90%) is:

Show for or five measurements???

• NB!!! If you established that the standard deviations of two sets of
data agree at a reasonable confidence level it is possible to proceed to
a comparison of the mean results derived from the two sets, using the t
test in one of its forms.
 Critical Values for the Rejection of Quotient Q

Number of Qcrit(Reject if Qexp > Qcrit)

Observations 90% Confidence 95% Confidence 99% Confidence
3 0.941 0.970 0.994
4 0.765 0.829 0.926
5 0.642 0.710 0.821
6 0.560 0.625 0.740
7 0.507 0.568 0.680
8 0.468 0.526 0.634
9 0.437 0.493 0.598
10 0.412 0.466 0.568
 The Application of Statistical Tests

The Analysis of Data

where xn is the questionable result in a set x1, x2, x3, . . . , xn.

Q is calculated for the questionable data and compared with a table of critical
values (Table???). The result is rejected if Q(experimental) exceeds Q(critical).

Exercise: (25.1 21.2 27.5 22.7 23.8 26.3 40.6 22.9)

One of the data set is an outlier in this set of data?

167 180 188 177 181 185 189
Test it at the 95% confidence Level (i.e. at an alpha level of 5%).
 EXERCISE

In a series of replicate analyses of a sample the following data (%) were

obtained:
 Exercise
Levels of Glucose at one of the George Mkhari hospital patient wards were monitored monthly to check diabetes. The glucose
concentration with patients with wildly elevated levels were monitored by using a Spectrophotometric analytical instrument
obtained from Chemistry department in the university within the hospital. The following results were found during a study to
check the effectiveness of the diet.

Time Glucose conc Mean glucose Sum of squares Standard

(mg/L) (mg/L) of deviations from deviation
Mean

January 1108,1122 1100.3 1687.43 16.8

1075,1099
1115,1083
1100

Help the hospital to calculate a pooled estimate of the standard deviation from the results and
February 992,975 996.2 1182.80 17.2
1022,1001
991
March 788,805 798.8 1086.80 16.5
779,822
800

April 799,745 771 2950.86 22.2

750,774
758

Help the hospital to calculate the pooled estimate of the standard deviation for
the method used by the university.
 Critical values for F at the 5% level

Degrees of freedom (numerator)

Degrees of freedom
(denominator) 3 4 5 6 12 20 ¥
3 9.28 9.12 9.01 8.94 8.74 8 .64 8.53
4 6.59 6.39 6.26 6.16 5.91 5.80 5.63
5 5.41 5.19 5.05 4.95 4.68 4.56 4.36
6 4.76 4.53 4.39 4.28 4.00 3.87 3.67
12 3.49 3.26 3.11 3.00 2.69 2.54 2.30
20 3.10 2.87 2.71 2.60 2.28 2.12 1.84
¥ 2.60 2.37 2.21 2.10 1.75 1.57 1.00
 Exercise
The technique of a trainee operator is being assessed by comparing his results
with those obtained by an experienced operator.
Question: Do the results obtained indicate a significant difference between the
skill of the two operators?

The trainee operator carried out six determinations yielding a mean of 35.25%
with a standard deviation of 0.34%. The experienced operator obtained a mean
of 35.35% and a standard deviation of 0.25% from five determinations.
 Use the F-test is used to compare the standard deviations

Fcrit from Table = 6.26 and there is no significant difference in the standard
deviations at the 95% level.

Equation (2.10) now enables the two means to be compared. If s is first

computed from the pooled data (equation (2.3)) and found to be 0.29% then

Conclusion: The probability of the difference in means being significant is very

low, and there is no difference between the skill of the two operators.
 The Nature and Origin of Errors
They usually originate from one of three major sources: operator error;
instrument error; method error. They may be detected by blank
determinations, the analysis of standard samples, and independent analyses
by alternative and dissimilar methods.

Errors may usually be classified as determinate or indeterminate.

Determinate: has a value which is (in principle at least) measurable and for
which a correction may be made. May be constant or proportional.
Indeterminate: fluctuate in a random manner and do not have a definite
measurable value. Have a fixed value and the latter increase with the
magnitude of the measurement.
Thus their overall effects on the results will differ.
These effects are summarized in Figure 2.1.
 Effects

The effects of constant and proportional errors on a measurement of

concentration.
 How to detect the determinate errors

Instrument errors: can be detected and corrected by calibration

Method errors: are particularly difficult to detect the best way is to analyze
standard reference materials, or use another and reliable analytical technique in
parallel with the method being evaluated, use blank determination for
detecting constant errors and vary sample in size

Personal errors: - can be minimized by care and self-discipline;

It is a good habit to check: (i) instrument readings, (ii) notebook entries, (iii)
calculations, etc.
 Significant figures in numerical calculations

For sums and differences:

The result contains the number of decimal places equal to the smallest
number of decimal places found in the expression

Example: 3.4 + 0.020 + 7.31 = 10.730

3.4 + 0.020 + 7.31 = 10.7

 For products and quotients

Use relative uncertainties of the numbers – select the largest and the
answer must have the same uncertainty.

The result contains the number of decimal places equal to the number of
decimal places in the absolute uncertainty of the expression

y = 24 x4.52/100.0
Answer: y = 1.08
 Rounding the results

NB!!! Postpone rounding until the calculation has been completed

•At least one extra digit beyond the significant digits should be carried through
all the computations in order to avoid a rounding error; this extra digit is called a
guard digit

•It is ordinarily sufficient to round the answer so that its relative uncertainty is of
the same magnitude as the relative uncertainty of the number with the largest
uncertainty

•It is important to remember that rounding decisions are an important part of

every calculation and that such decisions cannot be based on the number of digits
displayed on the readout of a calculator
 Definitions and Basic Concepts

True Result
The 'correct' value for a measurement which remains unknown except when a
standard sample is being analysed. It can be estimated from the results with
varying degrees of precision depending on the experimental method.

Accuracy
The nearness of a measurement or result to the true value that is Expressed in
terms of error.

Precision
The random or indeterminate error associated with a measurement or result.
Represented statistically by the standard deviation or relative standard
deviation
 Gravimetric Method of Analysis

Gravimetry: includes any analytical method in which the ultimate measurement

is by weight.

For Example:
(i) drying or heating of a sample in order to determine its volatile and non-
volatile components
(ii) possibly the sample might be distilled and the residue and fractions of
distillate weighed

Required Apparatus
Flasks, beakers, filter funnels, pipettes, filter crucibles, filter papers, oven,
muffle furnace, chemical balance, desiccator.
 Some Applications of Gravimetry

Analysis: of rocks, ores, soils, metallurgical and other inorganic samples for
their major components

NB!!! They are best suited to the determination of major constituents in

samples because of the practical limitations in accurately weighing quantities of
less than 0.1 g.
 Some Practical Gravimetric Procedures
Five stages:
Sample pretreatment; (dissolution of sample, separation or masking of
interfering ions)
Precipitation; ( from hot dilute solution, careful addition or homogeneous
generation of precipitating agent in small excess, with stirring: digestion)

eg. Magnesium may be precipitated from solution as MgNH4PO4 . 6H2O

Filtration;( cooled solution filtered, precipitate washed with dilute electrolyte
solution)

Drying and ignition; (careful drying at 110–140°C access of air during

ignition)

Weighing (weighings carried out to nearest 0.1mg reheating and reweighing

until constant weight is obtained; samples stored in a desiccator)
 NB!!!

This prevents simultaneous precipitation and reduces inclusion of impurities

Promotes particle growth and reduces occlusion. Again!!! digestion can

increase post-precipitation

Decreases solubility, reduces adsorbed impurities and prevents peptization

Prevents sputtering losses, ensures complete oxidation to a stoichiometric
product

Special care is needed for hygroscopic solids.

Major types of coprecipitation and their relation to the precipitate type

Type of coprecipitation Mode of contamination

isomorphic inclusion substitution of the precipitate lattice

with impurity ions of similar crystallinity

non-isomorphic inclusion solid solution of the impurity within

the precipitate
occlusion physical trapping of impurities
within precipitate particles

surface adsorption chemisorption of impurities from the

 Mechanism of PPT

2 Processes

Nucleation:
Particle growth:

Particle size and Filterability

RSS = Q - S/Q
 Further Reading

Skoog, D. A. & West, D. M., Fundamentals of Analytical Chemistry, CBS

College Publishing, New York, 1982.

Jefferey, G. H., Bassett, J., Mendham, J. & Denney, R. C. (eds) Vogel's Textbook
of Quantitative Inorganic Analysis (5th edn), Longman, London, 1989.
 Exercise:

In the analysis of 0.7011 of an impure sample containing chloride in one of the

laboratories from the Geology department at UP, 0.9805g of AgCl were
precipitated. Calculate the % by mass chloride in the sample obtained.

0.150 g of an alloy containing some magnesium was dissolved in a suitable

solvent. Magnesium oxinate was precipitated quantitatively, filtered, dried and
weighed. The weight of precipitate was 0.250g.
What was the percentage of magnesium in the original sample?
 Thermogravimetry Exercise

Thermal Analysis ( a branch of material Science where properties of materials are

studied as they change with Temperature)

• The thermogram for a 22.16 mg sample of MgC2O4•H2O shows two

steps: a loss of 3.06 mg from 100–250oC and a loss of 12.24 mg from
350–550oC. For each step, identify the volatilization product and the
solid residue that remains. Using your results studied earlier, explain
how you can use thermogravimetry to analyze a mixture containing
CaC2O4•H2O and MgC2O4•H2O.
• (You may assume that other components in the sample are inert and
thermally stable below 1000o C.)
 Stoichiometric calculations (2 lectures)

(a) Calculations involving mass, mole, millimoles, ppm, etc.

(b) Preparation of solutions with predefined concentrations

(c) Calculations involving dilution

(d) Expressing concentrations in different analytical units

(e) Calculations involving chemical stoichiometry

(f) P-function
 UNITS OF MEASUREMENT
 mole (SI mol): the Avogadro number 6.022 × 1023 of atoms or
molecules
 Molar mass (M) : mass (g) of 1 mol of an element or a substance

 Molar concentration (M) : number of moles of substance in 1L of

solution (mol/L)
a) analytical molarity: total number of moles of a solute in 1L
solution (c)
b) equilibrium molarity: molar concentration of a solute at
equilibrium, e.g. [HAc]

 Normality (N): number of equivalents of reagent in 1 L of a solution

 Percent concentration : express concentration in terms of fraction %

weight percent (w/w) : solute (g)/solution(g) x 100%

volume percent (v/v) : solute (mL )/solution(mL) x 100%

weight per volume percent (w/v) : solute(g)/ solution(mL) x 100%

parts per million (cppm) : solute(g)/solution(g) x 106ppm = 1 mg/kg

parts per billion (cppb) : ppb solute(g)/solution(g) x 109ppb = 1μg/kg

parts per trillion (cppt) : ppt solute(g)/solution(g) x 1012ppm =1ng/kg

pH : - log[H+]

pM : - log[M] where [M] refers to the molar concentration of a metal ion

 Exercise

Conversion of mass to moles

How many moles of benzoic acid (M = 122.1g/mol) are contained in 2.00g of

the pure acid?

Conversion of moles to mass

How many grams of Na+ (22.99 g/mol) are contained in 25g of Na2SO4
(142.0 g/mol)?
Analytical molar concentration.

Calculate the molar concentration of ethanol in an aqueous solution that

contains 2.30 g of ethanol (46.07 g/mol) in 3.50 L of solution.

Analytical and equilibrium molar concentrations.

Calculate the analytical and equilibrium molar concentrations of the solute species
in an aqueous solution that contains 285 mg of trichloroacetic acid, Cl3CCOOH
(163.4 g/mol), in 10.0 mL (the acid is 73% ionized in water).
Determine the mass of BaCl2·2H2O (MW = 244.3 g/mol) needed to prepare
500 mL of 0.0740 M Cl– solution. Describe the preparation of this solution.

Calculate the molar concentration of K+ of a 63.3 ppm solution of K3[Fe(CN)6]

(potassium hexacyanoferrate (III) or potassium ferricyanide).
Molar mass of K3[Fe(CN)6] is 329.24g/mol

Calculate the molar concentration of concentrated HNO3 solution that has a

specific gravity (density) of 1.42 g/cm3 and which is 70.5% (w/w) HNO3.
M(HNO3) = 63.0 g/mol.
 Titrimetry and Gravimetry
Titration: The overall procedure for the determination of the stoichiometric or
equivalence point.

Titrant: The solution added or reagent generated in a titration.

Titrand: The solution to which the titrant is added.

End Point: A point in the progress of the reaction which may be precisely located
and which can be related to the stoichiometric or equivalence point of the
reaction; ideally, the two should be coincident.
Indicator: A reagent or device used to indicate when the end point has been
reached.
Titrimetric method: the controlled reaction of a standard reagent in known
amounts with a solution of the analyte, in order that the stoichiometric or
equivalence point for the reaction between the reagent and the analyte may be
located.

Principles
Fast solution reactions between analyte and a reagent; titration to
stoichiometric point by volumetric or coulometric methods; end-point
detection by visual indicators, precipitation indicators or electrochemical
means.
Apparatus
Burettes, pipettes, volumetric flasks, analytical quality chemical balance,
indicator electrodes and coulometric generating electrodes.
 Complexometric Titrations

Ethylenediaminetetraacetic Acid (EDTA)

H4Y with H3Y–, H2Y2–,

 The Composition of Aqueous EDTA Solutions

,CL is the total amount of uncomplexed EDTA, given by:

NB!!! Now, it is convenient to evaluate a4, which may be done by substituting

into equation (5.11) from expressions for the dissociation constants K1, K2, K3, K4
Stability constant for the formation of EDTA – METAL complexes

Metal ion Kf MY
Mn2+ 6.2 x 1013
Ca2+ 5.0 x 1010
Ba2+ 5.8 x 107
Mg2+ 4.9 x 108
Ni2+ 4.2 x 1018
Cu2+ 6.3 x 1018
Zn2+ 3.2 x 1016
Pb2+ 1.1 x 1018
What reaction will you expect to occur if a solution containing Pb2+ is
added to a solution containing MgY2?

What reaction will you expect to occur if a solution containing Ba2+ is

added to a solution containing CuY2?
 Exercise

An EDTA titer value was determined using MgSO4 standard. A 50 mL aliquot of

solution containing 0.450 g of MgSO4 (FW 120.37) in 500 mL required 37.6 mL
of an EDTA solution to reach the end point. How many milligrams of CaCO3
(FW 100.09) will react with 1 mL of this EDTA solution?

Hamanskraal City water scientists took A 100ml aliquot of water and treated it
with a small amount of ammonia- ammonia chloride buffer to bring the pH to
10.After they added Calmagite indicator, the solution required 21. 46ml of
5.140 x 10-3 M EDTA for titration. As a specialist in EDTA complexometric
titration method, help the Scientists to calculate the hardness in terms of ppm
calcium carbonate using the Kf table given to you!