LECTURE NOTE

CHM 242
ANALYTICAL CHEMISTRY 1

COURSE LECTURERS:
DR TEMITOPE OSOBAMIRO &
DR ADEJUMOKE HASHIMI
 Course Content
One: Theory of Error
Accuracy and Precision
Error in chemical analysis
Significant Figures
Rules for computation of significant figures

Two: Statistical Treatment of Data

Measure of Central Tendency of Data
Measure of Spread of Data: Measure of Precision
Comparison of Results

Three: Sampling
Classes
Sampling process
sampling techniques
Sampler or sampling tool
Sample preservation
Four: Chemical Methods of Analysis
Titrimetric Methods
Types of Titrimetric Analysis
Standard Solution
Classes of Volumetric Analysis
Advantages of Titrimetric Analysis

Five: Gravimetric method

Types of gravimetric analysis
precipitation gravimetry-steps in gravimetric analysis
impurities in precipitate
Galvimetric calculations.
Advantages of gravimetric analysis
Introduction
Analytical chemistry is concerned with the chemical characterization of matter
and the answer to two important questions; what it (qualitative) is and how
much is it (quantitative).
Analytical Terms
Qualitative analysis: An analysis in which we determine the identity of the
constituent species in a sample.
Quantitative analysis: An analysis in which we determine how much of a
constituent species is present in a sample.

Analytes: The constituents of interest in a sample.

Matrix: All other constituents in a sample except for the analytes.

Precision and Accuracy
Precision describes the reproducibility of a result. If you measure a quantity
several times and the values agree closely with one another, your measurement
is precise. If the values vary widely, your measurement is not very precise.
Accuracy describes how close a measured value is to the “true” value. If a
known standard is available, accuracy is how close your value is to the known
value.
Errors in chemical analysis
Error: may be defined as a deviation from the absolute value or from the true average of a
large number of results. Error is defined as a difference between a computed, estimated, or
measured value and the accepted true value.
Types of Errors: 2 major types
1. Systematic errors (determinate errors or constant errors)
2. Random errors (indeterminate errors or accidental errors)
3. Gross /careless error
Systematic errors (determinate errors or constant errors): are due to well-defined
operational alteration in the analytical process
Characteristics of Systematic errors
They have a definite/ fixed value,
,, are reproducible
,, are often larger than random error
,, can be eliminated, avoided and corrected
,, are unidirectional
,, affect accuracy
Sources of Systematic errors
i. Instrumental Errors: are caused by non ideal instrument behavior, faulty calibrations
ii. Reagent Error: impurities in reagent used for analysis.
iii. Method Error: Errors inherent in a method of analysis. The non ideal chemical or
physical behavior of the reagents
iv. Operational and Personal Error: result from the carelessness, inattention, or personal
limitations of the analyst e.g. colour blindness
Ways of correcting Systematic Errors
1. Instrumental Errors: regular calibration
ii. Reagent Error: use of high quality reagents e.g. analaR grade, blank
determination
A blank contains the reagents and solvents used in a determination, but no analyte.
iii. Method Error: use of independent method, use of standard addition
iv. Operational and Personal Error: give the sample to a more proficient analyst
or using an automated procedure.
Random Error: arises from uncertainties and experimental fluctuations that are
unknown, uncontrollable and reveals as small scatters of results of replicate analysis.
Characteristics of random errors
They are randomly distributed
Not unidirectional
Not reproducible
Cannot be avoided
Affects precision
Gross/careless errors: are those due to mistakes that are not likely to be repeated in
similar determinations. Similar to systematic error but, larger in magnitude, can be
easily detected and avoided.
Significant Figures and Rounding
The number of significant figures in a measurement is the number of digits
known exactly plus one digit whose value is uncertain.
Convert each measurement to its equivalent scientific notation or decimal form.
a. 0.0120 mol HCl b. 605.3 mg CaCO3 c. 1.043×10−4 mol Ag
d. 9.3×104 mg NaOH
Rules for computation for Significant Figures
i. Observed quantities should be written with one uncertain figure
ii. In rounding off number, add 1 to the last figure retained if the following figure
is 5 or more
iii. For addition and subtraction, round the answer to the last decimal place in
common for each measurement in the calculation. The exact sum of 135.621,
97.33, and 21.2163 is 254.1673. Since the last decimal place common to all three
numbers is the hundredth’s place, round the result to 254.17.
135.621
97.33
21.2163
254.1673
Answer = 254.17
When working with scientific notation, first convert each measurement to a common
exponent before determining the number of significant figures.
For example, the sum of 6.17×107, 4.3×105, and 3.23×104
6.17 x 107
0.043 x 107
0.00323 x 107
6.21623 x107
Answer is 6.22×107.
iv. For multiplication and division, round the answer to the same number of significant
figures as the measurement with the fewest number of significant figures. For example,
when we divide the product of 22.91 and 0.152 by 16.302, we report the answer as 0.214
(three significant figures) because 0.152 has the fewest number of significant figures.
22.91×0.152 =0.2136 =0.214
16.302
Practice Question
How many significant figures are in each of the following measurements?
Convert each measurement to its equivalent scientific notation or decimal form.
a. 0.0120 mol HCl
b. 605.3 mg CaCO3
c. 1.043×10−4 mol Ag
d. 9.3×104 mg NaOH
2. Statistical treatment of data
Measure of Central Tendency of Data
Mean: The most commonly used parameter for representing the overall
properties of a number of measurements is the mean:
Range = the difference between the highest and lowest results.
Measure of Accuracy:
a. The absolute error Eabs, which is the difference between the true value (xtrue) and
the measured value (xi), can then be determined: Eabs = (xi - xtrue)

b.
 Statistical treatment of data
Measure of Central Tendency of Data
Mean: The most commonly used parameter for representing the overall properties
of a number of measurements is the mean:
Range = the difference between the highest and lowest results.
Measure of Spread of Data: Measure of Precision

Average deviation, i.e. the average difference, without regard to sign, of

each result in the series from the mean.
Standard Deviation: provides a measure of the spread of repeated
measurements either side of the mean. measure the dispersion or variability
of a large number of measurements
S=

Variance: is the square of standard deviation

Coefficient of variation (C.V): The lower the value the better the precision
Measure of Spread of Data: Measure of Precision
Average deviation, i.e. the average difference, without regard to sign, of
each result in the series from the mean.

Standard Deviation: provides a measure of the spread of repeated

measurements either side of the mean. measure the dispersion or variability
of a large number of measurements

Deviation
Weight (g) │Xi ─ X │ ( Xi ─ X )2
1.00 0.02 0.0004
0.98 0.00 0.0000
1.00 0.02 0.0004
1.05 0.07 0.0049
0.81 0.17 0.0289
0.98 0.00 0.0000
1.02 0.04 0.0016
Total Σ = 6.84/7 Σ = 0.32 Σ = 0.0362
Mean = 0.98 0.046
Variance: is the square of standard deviation

S=

Coefficient of variation (C.V): The lower the value the better the precision =

Confidence Interval (CI): This is used to estimate range within which the true mean
may be found.
Comparison of Results
Values obtained from a set of results are compared with either the
true value or with other sets of data to determine whether the
analytical procedure has been accurate or the result is precise.

T-test and F-test are used to answer the question- does

significantly differ from µ
X=Mean, µ=Accepted true value, s= standard
deviation, n=No of measurement
tcalc is then compared with ttab( from t-table) at specific confidence
limit
If tcalc is ≤ t-table (95 %) No significant difference
If tcalc is > t-table (95 %) There is significant difference

tcalc=
2. Sampling
Sampling is the process of reducing sample population to
representative sample that can be handled in the laboratory.
Classes of Analysis
i. In terms of sample size

ii. Classification based on analyte concentration: Major, Minor,

trace, ultra-trace
Samples are analyzed, but constituents or concentrations are
determined.
Sampling Process: involves- Obtaining background information
about the sample
Collecting a laboratory size sample from the bulk and reducing it to
test sample – Quartering and Coning
Types of Sampling
Simple random sampling: use of table of random
numbers
Stratified Sampling: for well organized samples, divide
into strata
Systematic Sampling: for homogenous and small bulk
sample
Sampler/Sampling Tools; Sampling tools must be clean
and appropriate
Sample Preservation: Physical, Chemical & Biological
Comparison of Results
Values obtained from a set of results are compared with either the true value or
with other sets of data to determine whether the analytical procedure has been
accurate or the result is precise.

T-test and F-test are used to answer the question- does significantly differ
from µ
X=Mean, µ=Accepted true value, s= standard deviation,
n=No of measurement
tcalc is then compared with ttab( from t-table) at specific confidence limit
If tcalc is ≤ t-table (95 %) No significant difference
If tcalc is > t-table (95 %) There is significant difference

tcalc=
A trainee in a medical lab will be released to work on her own when are
results agree with those of an experienced analyst at 95% confidence
limit. Result for a blood urea N2 analysis are below:Trainee,
s= 0.53mg/dl, N= 6, Analyst mean µ=13.95 mg/dl, given that t tab = 2.57

tcalc = 0.62 x 4.62 = 2.87> ttab = 2.57, there is significant difference in

the two results

So, the trainee cannot be released yet.

Practice Question
Analysis of Pb in Pb ore gave the following values in g:
0.72, 0.79, 0.78, 0.74, 0.76, 0.77. If the accepted true result
is 0.73 g. Determine whether there is significant difference
between the accepted result and the mean of the obtained
result.
Sampling
A sample is that portion of the physical environment which is withdrawn
for chemical analysis. It can be aqueous e.g industrial waste water,
gaseous (air) or solid (soil).
Types of Samples
i. Batch Sample: collecting sample from the environment and analyze
either on site or later in lab. Also called Grab samples, are collected at a
specific time and place.
ii. Continuous Sample: involves continous monitoring of the
environmental parameter of interest e.g effluent monitoring.
iii. Composite Sample: prepared by mixing several batch samples,
usually collected at the same place but, at different times e.g collection
of blood samples every two hours over a 24 hrs and pooled into one
container and analyzed.
Questions that need to be addressed before going for sampling:
When and where the sample should be taken
How many samples should be collected?
How much sample is required
Chemical methods of Analysis:
Two major methods:
1. Classical methods 2. Instrumental methods

Classical methods - two methods: Titrimetric and Gravimetric

methods
Titrimetric Methods of Analysis
Introduction
The term titrimetric analysis refers to quantitative chemical
analysis carried out by determining the volume of a solution of
accurately known concentration which is required to react
quantitatively with a measured volume of a solution of a substance
to be determined.

In titrimetric analysis the reagent of known concentration is called

titrant (Standard) and the substance being titrated is termed the
titrand.
For use in titrimetric analysis a reaction must have the
following conditions:
1- There must be a simple reaction which can be expressed by a
chemical equation; the substance to be determined should react
completely with the reagent in stoichiometric or equivalent
properties.
2- The reaction should be relatively fast. (Most ionic reaction
satisfies this condition.)
3- There must be an alteration in some physical or chemical
property of the solution at
the equivalence point.
4- An indicator should be available which, by a change in physical
properties (color or
formation of a precipitate), should sharply define the end point of
the reaction.
Definition of some terms
Titration: Titration is the process in which the standard
reagent is added to a solution of an analyte until the
reaction between the analyte and reagent is complete.

Equivalence point and End point

The equivalence point of a titration is a theoretical point
that cannot be determined experimentally. Instead, we can
only estimate its position by observing some physical
change associated with the condition of equivalence. This
change is called the end point for titration.
Titration error: The difference between the observed end point and the
true equivalence point in a titration.
Indicators: Indicators are often added to analyte solution in order to give
an observable physical change (end point) at or near the equivalence
point.
End Points in Volumetric Analysis
This involves the observation of some properties of the solution that
change in a characteristic way at or near the equivalent point. These
properties include:
1. Color due to reagent or an indicator substance.
2. Turbidity changes resulting from d formation or disappearance of solid
phase.
3. Electric conductivity of the solution.
4. Electric potential between a pair of electrodes immersed in the soln.
5. Refractive index of the solution.
6. Temperature of the solution.
7. Electric current passing through the solution
Primary standard
A primary standard is a highly purified compound that serves
as a reference material in all volumetric method. E.g
potassium hydrogen phthalate
properties of primary standard:
1- High purity.
2- Stability toward air.
3- Absence of hydrated water.
4- Ready availability at modest cost.
5- Reasonable solubility in titration medium.
6- Reasonably large molar mass
Secondary standard
A secondary standard is a compound whose purity has been
established by chemical analysis and serves as the reference
material for titrimetric method of analysis. e.g NaOH
Standard solution: is the reagent of exactly known concentration
used in titrimetric analysis

Desirable properties of standard solutions

1- be sufficiently stable so that it is only necessary to determine the
concentration once.

2- react rapidly with the analyte so that the time required between
additions of reagent is minimized .

3- react more or less completely with the analyte so that satisfactory

end points are realized.

4- Undergo a selective reaction with the analyte that can be

described by simple balanced equation.
Methods for establishing the concentration of standard
solutions: Two basic methods

Direct method: in which a carefully weighed quantity of

primary standard is dissolved in a suitable solvent and diluted to
an exactly known volume in a volumetric flask.
Standardization method: the process whereby the
concentration of a reagent is determined by reaction with a
known quantity of a second reagent.
Direct titration and back titration
When a titrant reacts directly with an analyte, the procedure is
termed a direct titration.
Back titration
An excess of amount of standard titrant is added to the analyte and the
excess unreacted standard is determined by back titration with a
second standard titrant.

Back – titration are often required when:

• the rate of reaction between the analyte and reagent is slow
•when the standard solution lacks stability.

Classification of Titrimetric Analysis: Four major classes

Complexometric Method
Precipitation Method
Redox “
Acid-Base “
Complexometric Titration
Complex formation serves as the basis of accurate and
convenient titration for metal ions in which the titrant is a
complexing agent. It is useful for the detm of many metals.

Many cations form complexes with a variety of substances that

have a pair of unshared electrons (e.g. N, O, S, atoms in their
molecules) capable of satisfying the co-ordination number of
the metals.

The metal ion is a lewis acid (analyte) – electron pair acceptor

The complexer (standard) is a lewis base – electron pair donor
Classification of Ligands: Two classes
Inorganic ligands such as water, ammonia, and halide ions,
Organic ligands such as 8-hydroxyquinoline.
A chelate is produced when a metal ion coordinates with two or more donor
groups of a single ligand to form a five or six member heterocyclic ring.

A ligand that has:

single donor group is called unidentate
two donor groups is called bidentate
three donor groups is called tridentate
four donor groups is called tetradentate
five donor groups is called pentadentate
six donor groups is called hexadentate
Tetradentate and hexadentate ligands have wider used because-
their reactions with cations are more complete
they tend to form 1:1 complexes.

A good example is ethylendiaminetetraacetic acid EDTA which is a

hexadentate ligand.
Chemistry and Properties of EDTA
It is a Lewis acid, has six binding sites (the four carboxylate groups and the two
amino groups), providing six pairs of electrons.
The actual number of coordination sites depends on the size of the metal ion;
however, all metal-EDTA complexes have a 1:1 stoichiometry.
six-coordinate metal-EDTA complex.

End Point detection

Indicator ---- (Chelating agents), they are usually dye of 0,0-dihydroxy azo
type.
Examples are: Erichrome black T--- It’s a weak acid, contains three ionizable H
atoms (H3In) used for Mg2+ with EDTA(red to blue). They are used for detection
of total hardness of water (i.e Ca2+ &Mg2+).
Xylenol Orange--- for titrating metal ions that form strong EDTA complexes,
titrated at pH 1.5-3.0.Titrating Bi, Zn, Co, Ni, Mn--- red-yellow to lemon yellow.
Zincon. Ca in presence of Mg blue red to orange.
End point- potentiometer
Example: Detm of water hardness with EDTA. Water hardness due to Ca2+
& Mg2+
Titrant-EDTA, Sample- Hard water, Indicator- Erichrome black-T,
Buffer the sample to pH10
Titration Ca2+ +H2Y2- ---- CaY2- + 2H+
Ca2+ + MgY2+----CaY2- + Mg2+
End point; Mg2+ +HIn2- ----MgIn- + H+
MgIn- + H2Y2----MgY2 +HIn2- + H+
Elimination of interfering substance
To remove Fe-add few crystals of KCN,
to remove Cu add few crystals of Hydroxylamine hydrochloride.
Color change; Wine red to purple to pure blue.
If Mg2+ is not present in the sample, add Mg-EDTA to the titration flask to
provide a sharp end point.
The metal indicator complex(MgIn-) should be 10 to 100 times less stable
than the metal-EDTA complex, For EDTA to displace it from the indicator, the
indicator cannot indicate the direct titration of Ca in the absence of Mg with
EDTA Why??
It forms too weak complex with Ca to give a sharp end point.
Types of EDTA Titration
Direct titration: The analyte solution (containing metal ion) is
buffered to the desired PH e.g 10,and titrated with the standard EDTA
solution
Back titration: Many metals cannot be titrated directly Why?
because
they precipitated in the pH range of titration,
form inert complexes
suitable indicator may not be available.
Excess standard EDTA solution is added, buffered to desired pH, then
the excess unreacted EDTA is back-titrated with a standard metal ion.

Replacement/Substitution Titration- used for metal that do not

react with metals indicator or for metal ions which form EDTA
complex that are more stable than other metals E.g. Mg &Ca. The
metal ion is first treated with Mg complex of EDTA
The amount of Mg ions displaced is equivalent to cation present and
can be titrated with standard EDTA solution and suitable metal
indicator.
Precipitation Titrations
Analyte and titrant react to form an insoluble precipitate. Titration with pptg
agents are useful for determining certain analytes, provided the equilibra are
rapid and a suitable means of detecting the end point is available.
In all argentometric titration(especially with adsorption indicator) strong light
should be avoided because light decomposes Ag salts.

The most common precipitation reaction is a metathesis reaction, in which two

soluble ionic compounds exchange parts. When a solution of lead nitrate is
added to a solution of potassium chloride, for example, a precipitate of lead
chloride forms.
Pb2+ (aq) + 2Cl-(aq) = PbCl2(s)
Methods for finding the end point in Precipitation Titration
1- Visual Indicator: There are two methods-
Indicators that forms coloured cpd with the titrant
-adsorption Indicators- Adsorbed on the ppt at equivalence point
Indicators that forms coloured cpd with the titrant:
Mohr method for Cl- using Ag+ as a
Titrant-Std AgNO3 Titrand - Cl-
Indicator: small amount of K2CrO4 to the solution containing the analyte,
Ag+ + Cl- = AgCl(s) White precipitate
2Ag+ + CrO42- = Ag2CrO4(s) Red precipitate
The concentration of the indicator should be kept low blw 0.002-0.005 M.
It is performed in slightly alkaline soln ≈ pH 8.
If too acidic, part of the indicator is present as HCrO4- and more Ag+ will be
required to form Ag2CrO4 ppt.

Volhard method : It is an indirect titration mtd for detg anions that form ppt
with Ag (Cl-, Br-, SCN-).
It is perform in acid (HNO3) soln.
is titrated with SCN- in the presence of Fe3+. The end point for the titration
reaction is the formation of the reddish colored Fe(SCN) 2+ complex.
SCN-(aq) + Fe3+(aq) = Fe(SCN)2+(aq)
The titration must be carried out in a strongly acidic solution to achieve
the desired end point.

Ist step: Cl- is ppted by a known excess quantity of std AgNO 3

AgCl is filtered and washed
Excess AgNO3 in the filtrate is detd by back titration with std KSCN
Ag+(aq) + SCN-(aq) = AgSCN(s)
End point is detected by adding Fe3+Ferric ammonium sulphate which
forms a soluble red complex with ist excess titrant.

Fajans' method, - adsorption indicator

For example, when titrating Cl- with Ag+

Indicator: the anionic dye dichloro-fluoroscein

Before the end point, the precipitate of AgCl has a negative surface charge
due to the adsorption of excess Cl-.
The anionic indicator is repelled by the precipitate and remains in solution
After the end point, the precipitate has a positive surface charge due to the
adsorption of excess Ag+.
The anionic indicator now adsorbs to the precipitate's surface where its color is
pink.

Eosin indicator is used for titration of Br-, I-, and SCN-. Itgives sharper end pt and
more sensitive than dichloro-fluoroscein but its not used for AgCl cause;

it binds more strongly with AgCl even before the particles becomes positively
charged.
Redox Titration
Volumetric analysis based on titration with reducing or oxidizing
agents.It is performed using visual indicator or by measuring the
potential with an appropriate electrode.

Detection of End pt
Measuring potential with an indicator electrode
Visual Indication- Three mtds
i. Self Indication- If the titrant is highly coloured, the colour may be
used to detect the end pt e.g KMnO4- deep purple to pink at end pt.
Self indicating rgts have the drawback that an excess of O.A is
always present at the end pt.
Correction: by- Blank detm
Perform standardization and detm under similar experimental
conditions.
ii. Starch Indicator: used for titration involving Iodine.
Before equivalence pt- Colourless
Beyond equivalence pt- dark-blue

iii. Redox Indicators: most types of redox titrations are

detected using redox indicators.
These are highly coloured dyes that are weak reducing or
oxidizing agents.
Unlike acid-base indicators, redox indicators depends on the
half-rxn potential rather than the completeness of the
titration or the sharpness of the end pt. e.g 1,10-
phenanthroline-iron(II) complex
[Ind]3+ + e- ( pale blue) = [Ind]2+ (deep red)
Methylene blue= Blue (oxid)→ Colourless (Redn)
Common Titrants: KMnO4 (Sec std), k2Cr2O7 (Pry std), Na2C2O4

Examples: Detm of Fe in Fe ore: Titrant: Std k2Cr2O7

Titrand: Fe ore dissolve in conc. HCI (Fe3+), this is reduced to Fe2+
Ind.: Na diphenylamine sulphonate- Colour change Green→ Violet red
Chemical Oxygen Demand (COD): Detm of the amount of O2 required
to oxidize all the organic materials in a sample of impure water e.g
industrial wastewater.
Titrant: Std k2Cr2O7 Titrand: water sample

Excess of Std k2Cr2O7 soln is added to the water sample and the amount
of unreacted Std k2Cr2O7 is back titrated with std ammonium Iron
sulphate soln.

Indicator: Diphenylamine blue→ green

Ferroin bluegreen → red brown
Titration with Iodine: two types
Iodimetry Iodometry

Iodimetry: involves the direct use of I2 (a moderately strong O.A)

to determine/titrate a R.A. This is called Iodimetric titration.
Titrant: Soln of I2 in KI
Titrand: Analyte R.A e.g SnCI2, H2SO3, H2S, Na2S2O3 in acid
medium

End pt detection: Starch indicator

The titration is performed in neutral/mild alkaline to weakly acid
solution. If the pH is too alkaline, I will disproportionate to
hypoiodate and Iodide
Iodometry: I2 generated in a reaction is titrated with the analyte
solution.

Example: detm of Cu in CuSO4

Analyte: CuSO4 dissolve in H2O

CuSO4 is made to react with KI, I2 is liberated

CuSO4 + 4KI≈ 2CuI + I2 + 2K2SO4

Generated I2 is titrated with std Na2S2O3

2CuSO4≡ I2 ≡ 2Na2S2O3
Detm of Dissolved Oxygen (DO)
The method was developed by Winkler,
it’s a measure of the amount of O2 available for the survival of aquatic
organism in H2O.
Also it’s the ability of H2O to oxidize organic impurities in wastewater.

DO is fixed at sampling pt to avoid loss with Mn(OH) 2, which rapidly &

quantitatively convert it to Mn(OH) 3
4Mn(OH)2 +O2 + H2O→ 4 Mn(OH)3
On acidification (H2SO4), the brown ppt Mn(OH)3 formed react with KI to
release I2
Mn(OH)3 + I- + H+ → Mn2+ + 1/2I2 + 3H2O

Generated I2 is detd by titrating with std Na2S2O3

2S2O32- + I2 → S4O62- + 2I-
O2 ≡ Mn(OH)3 ≡ 2I2 ≡ 4S2O32-
4 moles of 2S2O32- ≡ 1 mole of O2
Acid-Base Titration
Many inorganic and organic cpds are either acid/base and can be titrated
with std solutions of a strong acid/base.
Detection of End-pt:
1. Indicators: are weak acid/base that are highly coloured. Colour of
ionized form is markedly diff from non-ionized form.
Indicator with a pKa near d equivalence pt pH is usually use.
2. Mrt of pH at different pts of the titration expt (pH meter): end pt can
be detd by measuring the pH at diff pts of the titration. Plotting pH Vs
volume (mL) of titrant, end pt can be located.
Indicator Acid base
Methyl-orange red Yellow
Cresol-red yellow red

Phenolphthalein Colourless Violet

Volumetric Calculations
i. Standard Preparation: Salt- Pry Standard

Example: How many gms of Na2SO4 should be weighed out to

prepare 500 mL of a 0.100M solution.
Molar mass of Na2SO4 = 142g/mol
Molarity= Mass/Molar mass
Mass = 0.100 M x 142 g/mol = 14.2g/dm3

1000 mL contain 14.2 g

500 mL will contain = 500 mL x 14.2 /1000 = 7.1 g

Calculating Molarity of standard Acids
Example: How many mL of conc. H2SO4 acid, 94% (g/100 g soln),
density of 1.831 g/cm3 are required to prepare 1 Litre of a 0.100 M
soln.
From Density= mass/volume and Molarity = mass/molar mass
Molarity = % conc x density x 1000 mL/L = 0.940 x 1.831 x1000
Molar mass 98.1
=17.5 mol/L
To prepare 1 L of 0.100M, use dilution factor = C 1V1 =C2V2

C1=new conc, V1= new vol. (1000 mL), C2= original mol. =17.5 mol,
V2= volume to mre
0.1 x 1000 = 17.5 x V2
V2 = 0.1 x 1000 = 5.71 mL, measure 5.71 mL of acid and diluted to
17.5 mark with water
iii. Calculating the molarity of std soln
No of moles/Amount (mol) = mass (g)/ Molar mass
Mmole = mass (mg)/ millimolar mass(mg/mmole)
Molarity = Amount/Volume

Example: A 0.804 mg sample of an iron ore is dissolved in acid. The Fe is then

reduced to Fe2+ and titrated with 47.22 ml of 0.02242 M KMnO4 solution.
Calculate the result of analysis in term of a. percentage Fe.
Answers:
5Fe3+ + MnO4- + H+ ……. Mn2+ + 5Fe + 4H2O
5 : 1
Mmole (Amount) MnO4- = Molarity x Volume in ml = 0.002242 x 47.22ml
= 1.0587 mmole KMnO4.
1mole MnO4 = 5moles Fe
1.0587mmole = 5 x 1.0587mmole = 5.2934mmole.

Mmole = mass/ milli molar mass, Mass = mmole x milli molar mass
= 5.2934 x 0.055847 = 0.2956 mg of Fe.

% Fe = 0.2956 / 0.804 x 100% = 36.77%

Acid – Base Equilibra in Water
Acid/Base ionizes in water, the extent or amount of ionization depends
on the strength of the acid/base.
A strong electrolyte ionizes completely while a weak one ionizes
partially.
Examples of strong electrolytes are HCl, H2SO4, NaOH
while example of weak electrolytes are HC2H3O2 (acetic acid),
NH3,C6H5OH
Water ionizes slightly, that is, it undergoes autoprotolysis i.e. self
ionization of a solvent to give cation & anion.
H2O ↔ H3O+ + OH- Kw = H+ + OH-
Kw = thermodynamic constant
Kw = [H+] [OH-] = 1.0 X10-14 at 250C
pH = -Log [H+] pOH= -Log [OH-]
pkw = pH + pOH =14
Example 1: What is the concentration of OH-, if [H+] = 1.0 x 10-3 M.
Kw = 1.0 x 10-14 = (1.0 x 10-3) x (OH-)

[OH-] = 1.0 x 10-14 / 1.0 x 10-3

=1.0 x10-14 - -3 =1.0 x 10-11 M.

Example 2: Calculate the P(OH) and P(H) of 5.0 x 10-2M solution of

NaOH.
Answer: [OH-] = 5.0 x 10-2 M
pOH= -Log(5.0 x 10-2)
= 2 – 0.70 = 1.30
pH + pOH = 14
pH + 1.30 = 14
pH =14 – 1.3 =12.7
 Practise questions:
1. Calculate the pOH and pH of
(a.) 0.020 M HClO4, (b.) 1.2 x 104 M HNO3.

Example: Calculate the amount/concentration of a 2.0 ml strong acid

solution given its pH to be 3.00
pH = -Log[H+] = 3.00

Conc. of H+ = Antilog of 3 = 10-3 M

Note: Molariy = Amount/Volume

Amount in 2.0ml = 10-3 x 2.0 ml = 2 x10-3 mmol

Practice question: Calculate the amount of a strong base in 3.0ml

given its pOH = 10.0
 Very Dilute Solution
The above method is used when the concentration is high > 10 -6 M.
When the concentration is low, systematic equilibrium calculation is
used.
Contribution to acidity/basicity will be from both acid/base and water.
Example: Calculate the pH & pOH of a 1.0 x 10 -7 M solution of HCl.
Answer:
Equilibra: HCl → H+ + Cl-
H2O ↔ H+ + OH-
At equilibrium, [H+] water = [OH-]water = ϰ . 1.0 x 10-14
Total [H+] = [H+] + (ϰ) ………..1

Kw = 1.0 x 10-14 = [H+]total + [OH-]

[H+]total = 1.0 x 10-14 …….2

ϰ
Sub [H+]total in equation 1
= 1.0 x 10-14 = ConcHCl + ϰ
ϰ

1.0 x 10-14 = ϰ [Conc HCl] + ϰ

ϰ2 + 1.0 x10-7ϰ = 1.0 x 10-14

In quadratic format: ϰ2 + 1.0 x10-7ϰ - 1.0 x 10-14 = 0

A= ϰ2, b =1.0 x 10-7, c= 1.0 x 10-14

ϰ = 6.2x10-8 M →[H+]water
[H+]total = [H+]HCl + [H+] water

= 1.0 x 10-7 + 6.28x10-8

= 1.62 x 10-7 M

pH = -Log1.62 x 10-7 = 7 – 0.21 = 6.7

pOH = 14 – 6.7 = 7.21

Question: Calculate the pH and pOH of 2.4 x 10 -7 M HNO3.

 Weak Acid and Base
Weak acid/base ionize partially in water.
Ionization constant is used to calculate the amount ionized and from this, the
pH is calculated. The acidity constant for acetic acid at 25 degree Celsius is
1.75 x 10-5. HOAC ↔ H+ + OAC-

Ka = [H+] [OAC-] = 1.75 x 10-5 ……………..1

[HOAC]
When HOAC ionizes, it dissociates to equal portions of H + and OAC-
Example: Calculate the pH and pOH of a 1.00 x 10-3M solution of acetic
acid.
Conc: [HOAC] ↔ [H+] + [OAC-]
Initial: 1.00x10-3 0 0
@ Equil: 1.00x10-3 – ϰ ϰ ϰ
From the equation of Ka above,
(ϰ)( ϰ) = 1.75 x 10-5
1.00 x 10-3 - ϰ
If ˂ 10% or 15% of the acid is ionized i.e. Ka is smaller than 0.01 ϰ
The equation become; (ϰ2) = 1.75 x 10-5
1.00 x 10-3

ϰ2 = 1.00x10-3 x 1.75x10-5

ϰ = 1.32x10-4 M = [H+]

pH = -Log 1.32 x 10-4 = 4 – log1.32 = 4 – 0.12 = 3.88

pOH = 14 – 3.88 = 10.12

Question: The pH of an acetic acid solution is 3.26. What is the % acid

ionized?
Advantages
• Capable of a higher degree of precision and accuracy than instrumental
methods of
analysis.
• The methods are generally robust.
• Analyses can be automated.
• Cheap to perform and do not require specialized apparatus.
• They are absolute methods and are not dependent on the calibration of
an instrument.
Limitations
• Non-selective.
• Time-consuming if not automated and require a greater level of operator
skill than
routine instrumental methods.
• Require large amounts of sample and reagents.
• Reactions of standard solutions with the analyte should be rapid and
complete.