Lecture 10.

Analytical Chemistry
Basic concepts

1
 What is Analytical Chemistry ?

It deals with:
• separation
• identification
• determination of components in a sample.
It includes coverage of chemical equilibrium and
statistical treatment of data.
It encompasses any type of tests that provide
information relating to the chemical
composition of a sample. 2
• Analytical chemistry is divided into two areas
of analysis:

• Qualitative – recognizes the particles which

are present in a sample.

• Quantitative – identifies how much of

particles is present in a sample.

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• The substance to be analyzed within a sample
is known as an analyte, whereas the
substances which may cause incorrect or
inaccurate results are known as chemical
interferents.

4
Qualitative analysis

5
 Qualitative analysis is used to separate an
analyte from interferents existing in a sample
and to detect the previous one.
➢It gives negative, positive, or yes/no types of
data.
➢It informs whether or not the analyte is present
in a sample.

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Examples of qualitative analysis

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9
 Analysis of an inorganic sample
The classical procedure for systematic analysis of an
inorganic sample consists of several parts:
➢preliminary tests (heating, solubility in water, appearance
of moisture)
➢ more complicated tests e.g.
✓introducing the sample into a flame and noting the
colour produced;
➢determination of anionic or cationic constituents of
solute dissolved in water 10
 Flame test

Solutions of ions, when mixed with concentrated

HCl and heated on a nickel/chromium wire in a
flame, cause the flame to change to a colour
characteristic of the element.
Visible colours occur with the following ions:

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 Sodium Bright yellow (intense, persistent)

Potassium Pale violet (slight, fleeting)

Calcium Brick red (medium, fleeting)

Strontium Crimson (medium)
Barium Light green (slight)
Lead Pale bluish (slight, fleeting)

Copper Green or blue (medium, persistent)

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Flame test as qualitative analysis of cations

A B C

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15
 Physical appearance of inorganic salts
Salt Colour
MnO, MnO2, FeO, CuO, Co3O4,
1 Ni2O3; sulphides of Ag+, Cu+, Cu2+, Black
Fe2+, Co2+, Pb2+, Hg2+
2 Hydrated Cu2+ salts Blue
3 HgO, HgI2, Pb3O4 Red
4 Cr3+, Ni2+, hydrated Fe2+ salts green
5 Hydrated Mn2+ salts Light Pink
6 K2O, K2Cr2O7, Sb2S3, ferricyanides Orange
7 Hydrated Co2+ salts Reddish Pink
Chromates, AgBr, As2S3, AgI, PbI2,
8 Yellow
CdS
9 CdO, Fe2O3, PbO2, CuCrO4 Dark brown
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Determination of cation or anion
The procedure is based on treating the solution with
a succession of reagents which are specified to a
certain group of constituents.
The groups are then treated successively with
reagents that divide a large group into subgroups or
separate the constituents singly.
Portions of the material are dissolved separately, and
different procedures are used for each to detect the
cationic and anionic constituents.
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18
Analysis of organic compounds
The organic nature of a compound is generally indicated
by its behaviour on being heated in the air. Solids
usually melt, then burn with either a smoky or non-
smoky flame, in some instances leaving a black residue
of carbon.
The following elements are usually present in these
compounds: carbon, hydrogen, oxygen, nitrogen, sulfur,
occasionally, phosphorus, halogens, and some metals.
Specific tests are available for each of the individual
elements.

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Quantitative analysis

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• It determines number of moles or mass of particular
substance in a sample.

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• Quantitative data are inherently normally
expressed in a numerical format:
➢ the sign (negative or positive)
➢ the magnitude.
Both give the meaningful information.

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Scale of operations for analytical methods 23
Examples of quantitative analysis

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25
 Methods used in quantitative analysis involve:
▪ classical methods
✓gravimetric,
✓ volumetric,

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▪ Instrumental methods
➢ Electroanalytical (potentiometry, conductometry)
➢ Spectroscopic (UV-VIS, IR, AAS, FES)
➢ Mass spectrometry
➢ Methods involving radioactivity measurement
➢ Methods which involve both separation and quantitative
analysis (chromatography, electrophoresis)
➢ Other

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Classical methods of quantitative analysis

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Gravimetric analysis (gravimetry) is the quantitative

isolation of a substance by precipitation and weighing of the

precipitate.

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Procedure of gravimetric analysis:
➢Weigh the sample to be analyzed
➢Dissolve the sample in a suitable solvent, e g, water
➢Add an excess of the precipitating reagent to precipitate the
analyte
➢Filter the mixture to separate the precipitate from the solution
➢Wash the precipitate to remove any impurities
➢Dry the precipitate by heating to remove water
➢Cool the precipitate in a desiccator to prevent the precipitate
absorbing moisture from the air
➢Weigh the cooled precipitate
➢Repeat the drying and weighing process until a constant mass
for the precipitate is achieved
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Gravimetric analysis yields more accurate data about the
composition of a sample than volumetric analysis does.
However, the first one takes more time to perform in the
laboratory. Volumetric analysis in the other side doesn't
take that much time and the results that we obtain are in
the most cases satisfactory.

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Examples of gravimetric calculations
Calculate the mass of analyte in the sample.
General calculation of the percent by mass of analyte in a sample:
▪ Write the balanced chemical equation for the precipitation
reaction. E.g.
aA + bB → cC

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33
Calculation – working example
When an sample of impure potassium chloride (0.4500g)
was dissolved in water and treated with an excess of silver
nitrate. 0.8402 g of dry silver chloride precipitate was
obtained. Calculate the percentage KCl in the original
sample.

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KCl (aq)+ AgNO3(aq)→AgCl(S) + KNO3(aq)
Molecular mass of AgCl =142.5 g/mol
Molecular mass of KCl = 74.5 g/mol

0.8402 𝑔
Number of moles of AgCl = 𝑔 = 5.9 x 10-3 moles
142.5𝑚𝑜𝑙

Ratio between KCl and AgCl from balanced reaction is 1:1

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So the same number of moles of KCl reacted =
5.9 x 10-3 moles
Mass of KCl = 74.5 g/mol x 5.9 x 10-3 moles = 0.4396 g
0.4396 𝑔
% of KCl = ∙ 100% = 97.7%
0.4500 𝑔

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 Quiz
If 20.0 mL of 0.600 M BaCl2 reacts with 25.0 mL of 0.500
M H2SO4, the expected mass of BaSO4 produced is ...

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Sources of Error:
Reason of error result comparing with
real status
Incomplete precipitation too low percentage of
analyte
Incomplete drying of too high percentage of
sample analyte

Contamination of too high percentage of

precipitate with other analyte
ions

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There are two main areas of application for gravimetric
methods:
1. Analysis of standards to be used for the testing and
calibration of instrumental techniques.
2. Analysis requiring high accuracy, although the time
consuming nature of gravimetry limits this application to small
numbers of determinations.

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 Quiz
In a particular gravimetric analysis, the precipitate of
barium sulfate was balanced before it was completely
dried. The likely impact of this error on the calculated
result is ...
1. a higher result than the correct value.

2. minimal, because the calculation assumes a

hydrated sample is produced.

3. minimal, because the mass of water is likely to be

very low.

4. a lower result than the correct value.

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Volumetry (volumentric analys)

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Volumetric analysis (volumetry) can be simply a titration based on:
➢ a neutralization reactions between acid and base
➢ a precipitation reaction in which insoluble precipitate is
formed (argentometry)
➢ complexation – reaction between metal ions and standard
solution in which complex compounds are formed (titrant
e.g.EDTA- ethylene diamine tetra acetic acid).
➢redox- reaction between oxidizing agent and reducing agent.
Volumetric analysis is linked with instrumental determination of
equivalent point. 42
Rules of thumbs for successful volumetric analysis
▪The titrant should either be a standard or be standardized.
▪The reaction should proceed to a stable and well defined equivalence point.
▪The equivalence point must be able to be detected.
▪The titrant’s and sample’s volume or mass must be accurately known.
▪The reaction must proceed by a definite chemistry.
▪The reaction should be nearly complete at the equivalence point.
In other words, chemical equilibrium favours products.
▪The reaction rate should be fast enough to be practical.

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 Application of volumetric analysis
Volumetry analyses:
1. wastewater e.g. measure ammonia levels in
combination with other reactants to quantify other
chemicals present.
2. food products - help determine their nutritional
implications.e.g. acidity of the orange juice
3. improve wine production by measuring its acidity
4. pharmaceutical industry to ensure quality control or
to make the process more efficient.
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• 25 cm3 of sodium hydroxide is neutralized
exactly by 35 cm3 of 0.1 M hydrochloric acid.
What is the molarity of sodium hydroxide?

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 Quiz .
It’s true or false.
➢Standards is the reagent solution of known
conc. which is used to completely react with
the target analyte

✓ In volumetric analysis the volume of a reagent of

known conc. needed to completely react with the
target analyte is measured.

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Instrumental analysis

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• Instrumental methods involve analytical
measurements of some sample properties
(conductivity, electrode potential, light
absorption or emission, mass-to-charge ratio,
fluorescence etc.). These measurements are
made using instrumentation (equipment).

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Block diagram of an instrumental measurement
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 Applications of Instrumental Methods

1. Bioanalytical: biological molecules and/or

biological matrices (e.g., proteins, amino acids,
blood, urine)
2. Environmental: pesticides, pollution, air, water,
soil
3. Material science: polymers, characterization of
new materials
4. Forensic science (application of science to the
law): body fluids, DNA, gun shot residue, hair,
fibers, elemental analysis, drugs, alcohols,
poisoning, fingerprints, etc.
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Statistical treatment of data

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 Calibration of Instrumental Methods
▪ All types of analytical methods require calibration
for quantitation.
▪ Calibration is a process that relates the measured
analytical signal to the concentration of an
analyte.
▪ The three most common calibration methods are:
• Calibration curve
• Standard addition method
• Internal standard method

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 Calibration curve
• It is a general method for determining the
concentration of unknown sample by its
comparing the to a set of standard samples of
known concentration.
• It is also a plot of how the instrumental
response (analytical signal) changes with the
concentration of the analyte.

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Example of a calibration curve. The filled circles (•) are the individual
results for the standard samples and the line is the best fit to the data
determined by a linear regression analysis.

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 the region beyond the
Limit of Detection, or
where the detection
device becomes
overloaded with
incoming data.

The concentration of solute is

not intense enough to produce a The Linear Region where the
signal greater than background
response is proportional to the
noise of the instrument
concentration. As it increases,
response increases.
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▪ Detection Limit (Limit of detection, LOD): The minimum
concentration of an analyte that can be detected with a
specific method at a known confidence level.
LOD is determined by S/N, where, S/N = Signal-to-noise
ratio = (magnitude of the signal)/(magnitude of the
noise)
• Noise is unwanted baseline fluctuations in the absence of
analyte signal (standard deviation of the background)

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• The detection limit (LOD)is given by,
Cm = (Sm – Sbl)/m,
where, Cm = minimum concentration,
Sm = minimum distinguishable analytical signal
(i.e., S/N = 2 or S/N = 3),
Sbl = mean blank signal
m = sensitivity (i.e., slope of calibration curve)
• The amount of analyte necessary to yield a
net signal equal to 2 or 3x the standard
deviation of the background.
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▪ Dynamic range starts from the lowest concentration at
which quantitative measurements can be made (limit of
quantitation, or LOQ) and finishes at the highest
concentration at which the calibration curve starts to
depart from linearity (limit of linearity, or LOL).

The lower limit of quantitative (LOQ) measurements is

generally taken to be equal to ten times the standard
deviation of repetitive measurements on a blank (10 Sbl).

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Limit of detection and limit of quantitation via signal-to-noise.

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 Standard addition method
• The standard is added directly to the solution
of analyzed sample.
• This method is used in situations where
sample matrix also contributes to the
analytical signal. Such situation is known as
the matrix effect. It makes impossible to
compare the analytical signal between sample
and standard using the traditional calibration
curve approach.

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 Internal standard method
• The method of internal standards is used to
improve the precision of quantitative analysis. An
internal standard is a known concentration of a
substance that is present in every sample that is
analyzed. Internal standards can be used with
either the calibration curve or standard addition
methods, although the former is probably more
common.

https://facultystaff.richmond.edu/~cstevens/301/is_general.html
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• The purpose of the internal standard is to
behave similarly to the analyte but to provide
a signal that can be distinguished from that of
the analyte. Thus any factor that affects the
analyte signal will also affect the signal of the
internal standard to the same degree.
Therefore the ratio of the two signals will
exhibit less variability than the analyte signal.

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• Internal standards are often used in
chromatography, mass spectroscopy and
atomic emission spectroscopy. They can also
be used to correct for variability due to
analyte loss in sample storage and treatment.

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Describing method properties

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 Selectivity is a measure of a method’s freedom from
interferences. A selectivity coefficient, KA,I presents the
selectivity of a method for the interferent relative to the
analyte.

which may be positive or negative depending on the sign of

kI and kA. The selectivity coefficient is greater than +1 when
the method is more selective for the interferent than for the
analyte.

No analytical method is totally free from interference from other species,

and steps need to be taken to minimize the effects of these interferences.
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 The specificity of the test answers the question how the
method responds to the presence of a particular analyte. So
if a method is totally specific then it will respond only to the
analyte of interest and in this case no chemical interferents
will interfere with the analyte.
e.g. method is based on the reaction of various ions with
chloride ion. Silver ions are settled out when reacted with
chloride ion, whereas sodium forms soluble salt. Thus for the
mixture of Na and Ag ion adding Cl ion will be specific for the
identification of Ag ion.
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• The sensitivity of a test (method) describes how
close or similar in magnitude two readings may be,
and still be distinguished from each other.
• e.g. if the sensitivity of Pb2+ determination in some
method is 1 ppm - it means that we can distinguish
200 and 201 ppm, but 200.5 and 200.6 ppm is hard
to distinguish.

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Measurement Limitations (Uncertainty Analysis)
Measurements of chemical data have limitations. These
limitations are either inherent to the analytical equipment
performing the measurement or to the operator using the
equipment.
The precision describes the reproducibility of the data.
It is a measure of how carefully the result is determined without
reference to any true value (precision is related to uncertainty,
e.g., Δx)

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Three terms are used to describe the precision of a set of
replicate data: standard deviation, variance, and coefficient
of variation.
Standard deviation of the sample, s, describes the spread of
data around the mean value for a set of replicate measurement.

2
σ𝑁
𝑖=1 𝑋𝑖 − 𝑋𝑚𝑒𝑎𝑛
S=
𝑁−1

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• Variance – is an alternate measure, it is also
sometimes used as a measure of the reproducibility or
precision of technique.
• The variance = s2

• Coefficient of Variation ,Cv;

Cv = s/ mean value

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72
• Accuracy: How close the measurement
approaches the real value.
•

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 Quiz
• Calculate accuracy of the analysis (express it as the
relative error in terms of part per cent). The analysis
gives 115 ppm Fe and the true value is, in fact, 110
ppm Fe content.

• A) 15%; b)10%; c) 4.5%; d) 3.0%; e) 2.5%

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Question to be answered
1. What is the difference between qualitative and
quantitative analysis?
2. Consider the method in which the mixture of Cu2+; Pb2+
and Ag+ cations are determined by reaction with Cl- (the
result of this reaction is precipitate, but only silver chloride
is water insoluble). This method is specific with respect
to………ions, whereas it is not specific toward ……..

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 Calculations
• Replicate measurements for the lead content of a
water sample taken from a river gave the following
data.1) 19.4; 2) 20.6; 3) 18.7; 4) 19.2; 5) 21.6;
6) 18.9; 7) 19.9.
• Calculate the standard deviation of the data of Pb
content in ppm
• Mean result is 19.76 ppm

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 19.4 − 19.76 2 + 20.6 − 19.76 2 + 18.7 − 19.76 2 + 19.2 − 19.76 2 − ⋯…
𝑠=
6

𝑆 = 1.07 𝑝𝑝𝑚

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Signals which are employed in instrumental
methods of analysis are present in table below

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 Signal Instrumental Methods
Emission of radiation Emission spectroscopy
(X-ray, UV, visible, electron); fluorescence,

Absorption of radiation Spectrophotometry and photometry (X-ray, UV,

visible, IR)
Scattering of radiation Turbidimetry; nephelometry;
Refraction of radiation Refractometry;
Rotation of radiation Polarimetry; optical rotary dispersion; circular
dichroism
Electrical potential Potentiometry;
Electrical charge Coulometry
Electrical current Polarography; amperometry
Mass-to-charge ratio Mass spectrometry
Rate of reaction Kinetic methods
Thermal properties Thermal conductivity and enthalpy
Radioactivity Activation and isotope dilution methods 79
Review of some instrumental
methods

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 Electroanalytical methods
• They are a class of techniques in which the analyte amount is
determined by measuring the potential (V) and/or current (A)
in an electrochemical cell containing the analyte.
The main categories are:
• potentiometry (the difference in electrode potentials is
measured),
• coulometry (the cell's current is measured over time),
• voltammetry (the cell's current is measured while actively
altering the cell's potential).
• conductometry

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 Potentiometry
Method is based on the determination of the
potential differences between two half cells
(electrodes). Two half cells:
1. External reference electrode (ERE) – the
potential of this electrode is constant with
respect to that of the sample
2. The ion selective electrode (ISE)- „working
electrode” is composed of an internal reference
electrode (IRE) bathed in a reference solution
of the analysed analyte. The IRE is separated
from the sample solution by membrane,
selectively permeable to the analyte being
studied.

Saturated Calomel Electrode (SCE)

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Measuring Concentration using electrodes:
Working (indicator electrode) electrode is used with reference
electrode to measure potential of unknown solution
Ecell = EISE - EERE
• potential of ISE is proportional to measured ion activity
𝑅𝑇 𝑎𝑖 𝑠𝑜𝑙
𝐸 = 2.303 log
𝑧𝐹 𝑎𝑖 𝑟𝑒𝑓

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Electrodes can be
• specific (one ion)
• selective (several ions)
• simple
• complicated

84
 Electrode kind
Electrodes of the first kind. It responds directly to changing
activity of electrode ion e.g. Cu I Cu2+.
The equilibrium potential of this electrode is a function of the
concentration (more correctly of activity) of the cation of the
electrode metal in the solution.
In general, electrodes of first kind:
➢ simple
➢ not very selective
➢ some metals easily oxidized (deaerated solutions)
➢ some metals (Zn, Cd) dissolve in acidic solutions
85
 Electrode kind
Electrodes of the second kind - respond to changes
in ion activity through formation of complex.
Ag│AgCl│Ag+ or Ag│AgCl│Cl-
The potential of the metal is controlled by the
concentration of its cation in the solution, but this, in
turn, is controlled by the anion concentration in the
solution through the solubility product of the slightly
soluble metal salt.

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Example: Silver works as halide indicator electrode if coated
with silver halide.
Silver wire in KCl (sat'd) forms AgCl layer on surface

87
 Electrode kind
Electrodes of the third kind - respond to changes of
different ion than metal electrode.
The assembly consists of a metal in contact with two
slightly soluble salts (one containing the cation of the
solid metal, the other the cation to be determined, with
both salts having a common anion) immersed in a
solution containing a salt of the second metal (e.g.,
zinc metal--zinc oxalate--calcium oxalate--calcium salt
solution).
Zn │ZnC2O4│CaC2O4│Ca2+
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More complicated electrodes

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Membrane (Ion Selective) Electrodes:
Membrane:
• solids with low solubility
• semi-solids and polymers.
Some electrical conductivity - often by
doping.
Selectivity - part of membrane binds/reacts
with analyte.
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Types of membrane electrodes

91
• Non-crystalline membranes:
✓ Glass - silicate glasses for H+, Na+
✓ Liquid - liquid ion exchanger for Ca2+
✓ Immobilized liquid - liquid/PVC matrix for Ca2+ and NO3-

• Crystalline membranes:
➢ Single crystal - LaF3 for F-
➢ Polycrystalline or mixed crystal - AgS for S2- and Ag+

92
The glass pH electrode

2.3 ∙𝑅𝑇
E(pH) = E(constant) + ∙ log 𝐻 +
𝑛𝐹

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94
Enzymatic electrodes

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Crystalline Membrane Electrodes

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Crystalline Membrane Electrodes:
• Usually ionic compound
• Single crystal
• Crushed powder, melted and formed
• Sometimes doped (Li+) to increase conductivity
• Operation similar to glass membrane

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98
Potentiometric measurements are often used in routine
analyses because they are simple to achieve. The LOD of
the electrodes is in the range of 10−5–10−6 M. However,
the observed detection limit is governed by the presence
of interfering ions or impurities.

99
Some routine applications of the method are:
• in agriculture, the analysis of nitrates in soil samples
• in foodstuffs, the analysis of ions such as NO3−; F−;
Br−; Ca2+, etc. in drinks, milk, meat, or fruit juices
• in industry, the analyses of Cl- in paper paste, CN- in
electrolysis baths, Cl- and F- in galvanic processes
• in clinical chemistry, the analysis of certain ions in
serum and other biological fluids.
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101
 Quiz
• Describe the kind of electrode among the presented above
half cells:
1) Cu│Cu2+;
2) Ag │ Ag+
3) Hg│ Hg2Cl2 │ Hg+
4) Ag │AgCl │ Ag+
5) Zn  ZnC2O4 CaC2O4 Ca2+

102
 Voltammetric methods
• They determine components in the solution that
can be electrochemically oxidized or reduced.
• In these methods the potential is applied to the
sample via a conductive electrode (working
electrode) which is immersed in the sample
solution.
• The potential, which serves as the driving force,
is scanned over a region of interest. If at a
particular potential a component of the solution
is oxidized or reduced, then a current will flow at
the working electrode. 103
• The potential (E1/2) at which reduction or
oxidation of analyte occurs is characteristic of the
component (qualitative analysis). Whereas the
amount of current produced is proportional to
the concentration of that component in the
solution (quantitative analysis).

The polarogram of Cd determination

E1/2
104
Mercury-drop electrode.

105
• Voltammetric methods rank among the most
sensitive analytical techniques available. They
are routinely used for the determination of
electroactive inorganic elements and organic
substances in nanogram and even picogram
amounts; often the analysis takes place in
seconds.

106
Conductometry

107
108
Solutions that contain ionic species conduct electricity.

109
Conductivity in water is affected by the presence of
inorganic dissolved solids which consist of:
▪ anions (Cl-, NO3-, SO42-, and PO43-)
▪ cations (Na+, Mg2+, Ca2+, Fe3+, and Al3+).
Organic compounds like oil, phenol, alcohol, and
sugar do not conduct electrical current very well and
therefore have a low conductivity when in water.

110
Conductance can be defined as the reciprocal of resistance
which means that the conductance of an electrolytic solution
is simply the reciprocal of its electrical resistance.
Usually, conductance is given the symbol G and given the
units of ohm-1 or, in SI units, the siemens (S).

111
K = kappa; conductivity

C = concentration in M

112
✓ Specific conductivity it is a conductivity offered by
a substance of 1cm length and 1sq.cm surface area.

✓ Equivalent conductivity it is a conductivity offered by

a solution containing equivalent weight of solute in it.

✓ An equivalent ionic conductance of an ion is defined as its

molar conductance divided by the charge on the ion
(positive or negative).

113
 Factors affecting conductivity

• Temperature
• Ion size
• Number of ions (concentration)
• Ion charge

114
Resistance

Fig. Resistance of solution vs. temperature

115
 Molar conductance (Λm) of various ions at infinite
dilution at 25℃
ions molar conductance
K+ 73.52
Na+ 50.11
Li+ 38.69
H+ 349.82
Ag+ 61.92
Cl- 76.34
Br- 78.40
OH- 198.00

DWIVEDI ASHISH
116
 18
o
Temperatura 18oCC
Temperature 18 NaOH KOH
16

14

Konduktywność [S/cm]
NH3
12

10 MgCl2
Conductivity

8 NaCl
6
Na2SO4
4

2 CO2
0
0 1 2 3 4
Concentration 3
Koncentracja [mg/dm ]

Fig. Relationships concentration of electrolytes vs. conductivity

117
 Square root from the solute concentration

Fig. Electrolyte equivalent conductivity vs. concentration

of electrolyte (presented as the square root of concentration).
118
Tab. 1. Molar conductivity vs concentration relationships for chosen electrolytes.

Molar conductivity of some solution  [cm2S/mol]

25C
C HCl NaCl KCl
[mol/dm3]
0.0005 422.53 124.44 147.74
0.001 421.15 123.68 146.68
0.005 415.59 120.59 143.48
0.01 411.80 118.45 141.09
0.05 398.89 111.01 133.30
0.1 391.13 106.69 128.52
0.5 360.7 93.70 117.41
1 332.2 85.88 112.05
5 167.4 49.5 -
10 70.7 - -
119
The molar conductivity (Λm) of a strong electrolyte varies
with molar concentration in accord with the empirical law
discovered by Friedrich Kohlrausch in 1876:

m =  − K c o
m
Λm0 - the limiting molar conductivity, is the molar conductivity in the limit of
such low concentration that the ions no longer interact with one another.
The constant K takes into account the effect of these interactions when
the concentration is nonzero

120
When the ions are so far apart that their interactions
can be ignored, we can suspect that the molar conductivity
is due to the independent migration of cations in one direction and
of anions in the opposite direction, and write

 = + +  −
o
m

121
 Tab. 2. Limiting ions conductivity
Cation Anion
o o [ S  cm 2 ]
 [ S  cm ]
2

H+ 349.82 OH- 197.60

Li+ 38.70 Cl- 76.34
Na+ 50.10 Br- 77.70
K+ 73.50 J- 76.85
Ag+ 61.90 NO3- 71.46
Mg2+ 106.12 C 2 O 24− 40.90

Ca2+ 122.00 SO42- 159.60

Ba2+ 130.00 CO32- 166.60

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 Calculations
• Determine the limiting molar conductivity of CaCl2 if
the limiting ion conductivity of Ca2+ (λ0 = 122.50 S
cm2) and Cl-1 (λ0 = 76.32 S cm2).

Λ0 of CaCl2 = λ0 Ca + 2 λ0 Cl = [122.50 + 2 (76.32)] S cm2

= 275.14 S cm2

123
Determination of solute properties

124
• Degree of dissociation
Λ
𝛼=
Λ0

𝑚𝑜𝑙𝑎𝑟 𝑐𝑜𝑛𝑑𝑢𝑐𝑡𝑎𝑛𝑐𝑒 𝑎𝑡 𝑎 𝑔𝑖𝑣𝑒𝑛 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛

=
𝑚𝑜𝑙𝑎𝑟 𝑐𝑜𝑛𝑑𝑢𝑐𝑡𝑎𝑛𝑐𝑒 𝑎𝑡 𝑎𝑛 𝑖𝑛𝑓𝑖𝑛𝑖𝑡𝑒 𝑑𝑖𝑙𝑢𝑡𝑖𝑜𝑛

125
For acids and bases the concentrations
can be calculated when the value(s) of the acid dissociation
constant(s) is(are) known.
𝐶 ∙𝛼 2
𝐾𝑎 =
1−𝛼
For a monoprotic acid, HA, dissociation constant Ka is linked
with molar conductivities by:

126
• Limiting molar conductivity of some weak
organic acid water solution is equal to 402,0
S cm 2 mol -1. 0.1 M solution of the same acid
has molar conductivity equal to 15,1 S cm2
mol -1. Calculate:
• a) dissociation degree of this acid
• b) dissociation constant K of this acid

127
Conductivity can be also used for the
determination of:

➢ Solubility of sparingly soluble salts

➢ Ionic product of water
➢ Basicity of organic acids
➢ Salinity of sea water (oceanographic work)
➢ Chemical equilibrium in ionic reactions
➢ Conductometric titration

128
Applications
Conductivity measurements are used extensively in
many industries to monitor quality in:
➢ public water supplies,
➢ in hospitals,
➢ in boiler water
➢ industries which depend on water quality such as
brewing.
➢ Conductivity detectors are commonly used with
ion chromatography

129
Checking purity of water
Table of Aqueous Conductivities
Solution µS/cm mS/cm ppm

Totally pure water 0.055

Typical DI water 0.1
Distilled water 0.5
RO water 50-100 25-50

Domestic "tap" water 500-800 0.5-0.8 250-400

Potable water (max) 1055 1.055 528

Sea water 56,000 56 28,000
Brackish water 100,000 100 50,000
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 Quiz
Conductivity is defined as
• A) the ability of a substance to repel electric
current.
• B)the ability of a substance to conduct electric
current, which is the same as resistivity.
• C) the ability of a substance to conduct electric
current, which is the reciprocal of resistivity.
• D) the ability of a substance to conduct variable
resistance.

131
http://ga.water.usgs.gov/edu/electrical-conductivity.html

132
Biosensors

133
http://www.intechopen.com/books/biosensors-emerging-materials-and-
applications/development-of-potentiometric-urea-biosensor-based-on-canavalia-
ensiformis-urease 134
Glucose sensors
135
Fig. Continuous monitoring of metabolites in saliva using mouthguard
provides instant information about health, fitness and stress of the wearer.

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Sensors 2017, 17(9), 2128; doi:10.3390/s17092128

137