THE UNIVERSITY OF DODOMA

COLLEGE OF NATURAL AND MATHEMATICAL

SCIENCES (CNMS)
DEPARTMENT OF CHEMISTRY
CH 1102:
Basic Analytical Chemistry
LECTURE 7
Instructors : Dr. Ismail A. Msangi & Joseph M. Fugo
Phone : +255 625 973 343
Email : [email protected]
 LECTURE 7 OUTLINES
1. Electrochemistry and Potentiometric
titration.

2. Gravimetric Method of Analysis.

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Introduction to electrochemistry and Potentiometric titration
 Electrochemistry - is the branch of chemistry which deals with the study
of relationship between electrical energy and chemical
energy and interconversion from one form into another.
 Electrochemistry is the study of electron movement in an oxidation or
reduction reaction at a polarized electrode surface.
 Each analyte is oxidized or reduced at a specific potential and the current
measured is proportional to concentration.
 When a chemical reaction is driven by an electrical potential difference, as
in electrolysis, or if a potential difference results from a chemical reaction
as in an electric battery or fuel cell, it is called an electrochemical reaction.
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 In this reactions, electrons move via an electronically-conducting phase
between electrodes separated by an ionically conducting and electronically
insulating electrolyte.
 Unlike in other chemical reactions, in electrochemical reactions electrons
are not transferred directly between atoms, ions, or molecules, but via the
aforementioned electronically-conducting circuit.
 This phenomenon is what distinguishes an electrochemical reaction from a
conventional chemical reaction
 Electrochemistry is the study of chemical processes that cause electrons to
move.

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 This movement of electrons is called electricity, which can be generated by
movements of electrons from one element to another in a reaction known as an
oxidation-reduction ("redox") reaction.
 A redox reaction is a reaction that involves a change in oxidation state of one or
more elements.
 When a substance loses an electron, its oxidation state increases; thus, it is
oxidized.
 When a substance gains an electron, its oxidation state decreases, thus being
reduced.
 Therefore. electrochemistry is the study of electricity and how it relates to
chemical reactions.

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 Redox reaction
 The term "redox" stands for reduction-oxidation.
 It refers to electrochemical processes involving electron transfer to or from
a molecule or ion, changing its oxidation state.
 This reaction can occur through the application of an external voltage or through the
release of chemical energy.
 Oxidation and reduction describe the change of oxidation state that takes place in the
atoms, ions or molecules involved in an electrochemical reaction.
 Formally, oxidation state is the hypothetical charge that an atom would have if all
bonds to atoms of different elements were 100% ionic.
 An atom or ion that gives up an electron to another atom or ion has its oxidation state
increase, and the recipient of the negatively charged electron has its oxidation state
decrease.
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Oxidation

• The loss of electrons from an atom or molecule.

• The atom or molecule which loses electrons is known as the reducing agent, or
reductant.
• Thus, the reducing agent is always being oxidized.
Oxidation may also be defined as:
 the gain of oxygen
 the loss of hydrogen
 Increase in oxidation state

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Reduction

• The gain of electrons from an atom or molecule

• The substance which accepts the electrons is called the oxidizing agent, or
oxidant.
• Thus, the oxidizing agent is always being reduced in a reaction.
Reduction may also be defined as:
 the loss of oxygen
 the gain of hydrogen
 Decrease in oxidation state

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 Electrochemical Cell
 An electrochemical cell is a device that produces an electric current from
energy released by a spontaneous redox reaction.
 Electrochemical cells have two conductive electrodes (the anode and the
cathode).
 The anode is defined as the electrode where oxidation occurs and the cathode
is the electrode where the reduction occurs.
 Electrodes can be made from any sufficiently conductive materials, such as
metals, semiconductors, graphite, and even conductive polymers.
 In between these electrodes is the electrolyte, which contains ions that can
freely move.
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Types of electrochemical cell

 Electrochemical cell are of two types

(i) Galvanic cell

(ii) Electrolytic cell

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(i) Galvanic cell
 The galvanic cell converts chemical energy into electrical energy i.e. electricity can be
obtained with the help of redox reaction e.g. battery (galvanic cell in series).
 The oxidation and reduction take place in two separate compartments.
 Each compartment consists of an electrolyte solution and metallic conductor which acts
as an electrode.
 The compartment containing the electrode and the solution of the electrolyte is called
half cells.
Example: - Daniel cell in which zinc and copper are used for a redox reaction to take
place.
i.e. Zn(s) + Cu2+(aq) → Zn2+ + Cu(s)
 At anode (oxidation half): Zn(s) → Zn2+ + 2e–
 At cathode (reduction half): Cu2+(aq) + 2e– → Cu(s)
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• A Daniel cell (Galvanic cell)

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• General
composition
of Galvanic
cell

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 Galvanic cell containing a Salt bridge which is usually an inverted U-
tube filled with a concentrated solution of inert electrolytes.
 The salt bridge helps:
– to maintain the charge balance in a cell
– to complete the circuit by allowing the flow of ions through it.
 It contains a gel in which inert electrolytes (e.g. KNO3 or K2SO4) are
mixed.
 Through the salt bridge, negative ion flows towards the anode and
positive ion flow to the cathode and the charge balance is maintained and
cell keeps on functioning.

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 In a galvanic cell, when two-electrode are dipped in their respective ion;
– there is a tendency of one of the electrodes (anode) to undergo oxidation
– whereas the ion of the other electrode (cathode) has the tendency to gain an
electron.
 This tendency of losing of electrons (oxidation) or gaining of electrons (reduction)
create potential difference called electrode potential.
 The electrode potential of an electrode relative to standard hydrogen electrode
under standard conditions is called Standard electrode potential.
 The standard conditions taken are:
1 molar concentration of each ion in the solution.
A Temperature of 298 K.
1 bar pressure.
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 When the electrodes in contact with their ions are arranged on the basis of the
values of their standard reduction potential or standard oxidation potentials, the
resulting series is called the electrochemical series.

 Electrochemical series is the arrangement of various elements in the order of

decreasing or increasing value of standard reduction potentials (measured at 298
K, 1M concentration of ions and 1 atmospheric pressure.

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• Electrochemical series
Half-reactions 𝑬𝒐 (Volts)
F2(g) + 2e- → 2F-(aq) +2.87
Au+(aq) + e- → Au(s) +1.69
Ce4+(aq) + e- → Ce3+(aq) +1.61
MnO4-(aq) + 8H+ + 5e-→ Mn2+(aq) + 4H2O(l) +1.51
Cl2(g) + 2e- → 2Cl-(aq) +1.36
Cr2O72-(aq) + 14H+(aq) + 6e- → 2Cr3+(aq) + 7H2O(l) +1.33
Ag+(aq) + e- → Ag(s) +0.80
Fe3+(aq) + e- → Fe2+(aq) +0.77
Cu2+(aq) + 2e- → Cu(s) +0.34
2H+(aq) + 2e- → H2(g) 0
Fe3+(aq) + 3e- → Fe(s) -0.04
O2(g) + H2O(l) 2e- → HO2-(aq) + OH-(aq) -0.08
Pb2+(aq) + 2e- → Pb(s) -0.13
Sn2+(aq) + 2e- → Sn(s) -0.14
Fe2+(aq) + 2e- → Fe(s) -0.44
Zn2+(aq) + 2e- → Zn(s) -0.76
Al3+(aq) + 3e- → Al(s) -1.66
Mg2+(aq) + 2e- → Mg(s) -2.36

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 In the galvanic cell there are two half cell,
– the oxidation half-cell( anode) and
– the reduction half -cell( cathode).
 Due to the difference in the potentials of these half-cells, the electric current
moves from the electrode of higher potential (cathode) to the electrode of lower
potential( anode).
 The difference between the electrode potential of the two half cell is called cell
potential or emf of a cell.
Eocell = Ecathode – Eanode
Ecathode = standard reduction potential of the cathode.
Eanode = standard reduction potential of the anode.
 If Eocell is positive then the reaction is feasible.
 If Eocell is negative then the reaction is not feasible.
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Example:
Calculate e.m.f of the cell Ni/Ni2+,1 M//Cu2+/Cu, 1 M, Given that E°Ni2+/Ni
= -0.25 V and E°Cu2+/Cu = 0.34 V (reduction potentials)
Solution:
e.m.f = Ered (cathode) – Ered (Anode)
= 0.34 V – (-0.25) V
= 0.34 V + 0.25 V
= 0.59 V

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Half-cell potential (single electrode potential)
 When a strip of metal (M) is brought in contact with the solution containing its
own ions (Mn+) a half cell or a single electrode is formed.
 The electrochemical potential difference sets up between the metal and solution of
its ions is known as half-cell electrode potential.
 The half cell potential of an electrode can be determined relative to the standard
hydrogen electrode.
 Because every cell consists of two half-cells, it is not possible to measure the
potential directly. However, if the tendency of a certain half-reaction is assigned to
be zero, then the tendencies of all other half-reactions can be determined relative
to this reference half-reaction. For that reason the half-reaction 2H+ + 2e- → H2
is the reference half-reaction with the standard reduction potential of 0.0000 V.

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Sign convention

 The reduction potential of a half-cell is given a (-ve) sign when the half
cell reaction involves oxidation, when connected with a standard
hydrogen electrode and a (+ve) sign when the half cell reaction involves
reduction, when coupled to the standard hydrogen electrode.

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Determination of cell Potential

 The standard reduction potentials, E° of half reactions involved in an

electrochemical cell determines the tendency for an overall redox reaction to
occur.
 The more the two half reactions are separated for E°, the greater is the tendency
for the net reaction to occur.
 The overall potential or cell potential is symbolized by E°cell.
 The general steps for determining cell potential are presented and illustrated
considering the following cell equation.
Cu(s) + Ag+(aq) → Ag(s) + Cu2+(aq)

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• Step 1: Write the equations representing the half-reactions as extracted from
the overall reaction given and label as an oxidation and a reduction.
Oxidation: Cu(s) → Cu2+(aq) + 2e-
Reduction: Ag+(aq) + e- → Ag(s)
• Step 2: locate half-reactions as in electrochemical series and write the E°
values adjacent to the respective half-reaction. For oxidation half-
reaction, the sign of the E must be changed since the reactions are written
in reverse.
Oxidation: Cu(s) → Cu2+(aq) + 2e- E° = - 0.34 V
Reduction: Ag+(aq) + e- → Ag(s) E° = + 0.80 V
(note the change in sign for the oxidation half-reaction)

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• Step 3: Balance charges, equalize electrons in half-reactions and add the two
equation and E° values together. Do not multiply the E° values by the
multiplying coefficients. The result is E°cell.
Oxidation: Cu(s) → Cu2+(aq) + 2e- E° = - 0.34 V
Reduction: 2Ag+(aq) + 2e- → 2Ag(s) E° = + 0.80 V
_____________________________________________________________________________

Cu(s) + 2Ag+(aq) → 2Ag(s) + Cu2+(aq) E°cell = + 0.46 V

• Step 4: If is E°cell positive (+), the reaction proceed spontaneous to the right as
written, If is E°cell negative (-), it will proceed spontaneous to the opposite
direction i.e. to the left.
• Since E°cell is positive (+), the reaction proceed spontaneous to the right as
written.
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(ii) Electrolytic cell
 The electrolytic cell converts electrical energy to chemical energy.
 Here the electrodes are dipped in an electrolytic solution containing cations and
anions.
 On supplying current the ions move towards electrodes of opposite polarity and
simultaneous reduction and oxidation take place.
Example:
In the electrolysis of molten sodium chloride, sodium chloride is melted (above
801oC), two electrodes are inserted into the melt, and an electric current is passed
through the molten salt.

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The chemical reaction that takes place at the electrodes are:
• Sodium-ion migrates to the cathode, where sodium ion gains one electron and
reduce to sodium metal.
Na+ + e– → Na
• Chloride ions migrate towards the anode where it loses one electron and gets
oxidised to chlorine gas.
Cl– → 1/2Cl2 + e–
• The overall reaction is the breakdown of sodium chloride into its elements
2NaCl → 2Na(s) + Cl2(g)

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• Electrolysis
of molten
sodium
chloride

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 In electrolytic cell, when there are more than one cations or anion the process of
discharge becomes competitive in nature.

Example:
 In the electrolysis of NaCl solution, apart from Na+ and Cl– ions the solution of
sodium chloride also contains H+ and OH– ions due to ionisation of water.
 When the potential difference is applied between the two electrodes, Na+ and H+
ions move towards the cathode and Cl– and OH– ions move towards the anode.
 At cathode H+ ions get reduce in preference to give hydrogen gas because
hydrogen has a higher reduction potential than sodium.
 At the anode, Cl– ions are oxidised in preference to OH– to give chlorine gas.

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• Electrolysis of
sodium chloride
solution

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Cell Notation
 Cell notation - is a shorthand method of expressing a reaction in an
electrochemical cell.
 It is a shorthand notation to represent the redox reactions of an electrical cell.
 A cell notation has a double vertical line (||) used to separate the anode half
reaction from the cathode half reaction. This represents the salt bridge.
– The anode (where oxidation occurs) is placed on the left side of the (||).
– The cathode (where reduction occurs) is placed on the right side of the (||).
 A single vertical line (|) is used to separate different states of matter on the same
side, and a comma (,) is used to separate like states of matter on the same side.

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Example:
• For the Daniel cell discussed previously with the half reaction
Zn(s) → Zn2+(aq) + 2e−
Cu2+(aq) + 2e− → Cu(s)

• The cell notation will be;

Zn(s)/Zn2+(aq)//Cu2+(aq)/Cu(s)
• Moreover the cell notation for the iron and silver electrochemical cell may be
written as;
Fe2+(aq),Fe3+(aq)//Ag+(aq)/Ag(s)

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Homework
1) Write the cell diagram for this reaction:
Cu(s) + 2Ag+(aq) → Cu2+(aq) + 2Ag(s)

2) Write cell reactions for this cell diagram:

Al(s)/Al3+(aq)//Sn2+(aq)/Sn(s)

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The Nernst Equation
 Nernst equation is the mathematical expression that gives a quantitative
relationship between the concentration of ions and electrode potentials
 For general reduction reaction of an electrode:
Mn+ + ne- → M
 The Nernst equation is presented as
° 𝑅𝑇 ° 2.303𝑅𝑇
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑒𝑙𝑙 − ln 𝑄 or 𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑒𝑙𝑙 − log 𝑄
𝑛𝐹 𝑛𝐹

𝑅𝑇 [𝑀]
Therefore E = 𝐸° − ln 𝑛+
𝑛𝐹 [𝑀 ]

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 Nernst equation is derived from the Gibbs free energy
i.e. ∆G = ∆G° + RTln Q
 But for the electrochemical,
∆G = –nFE and ∆G° = –nFE° (at standard condition)
 Hence, from ∆G = ∆G° + RTln Q
–nFE = –nFE° + RTln Q
 By dividing the whole equation by – nF,
RT
E = E° – ln Q _____ Nernst equation
nF

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• Nernst equation can also be presented using “log” instead of “ln”
NB: ln = 2.303 log
RT
• From E = E° – ln Q
nF
2.303RT
E = E° – log Q ______ Nernst equation
nF

2.303 x 8.314 x 298

• At 25°C, E = E° – log Q
n x 96500

0.0592
E = E° – log Q
n

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Example:
You have an electrochemical cell with lead and silver running at 25°C. the reaction of
the cell is
Pb(s) + 2Ag+(aq) → Pb2+(aq) + 2Ag(s)
Calculate the cell potential when [Ag+] = 0.75 M and [Pb2+] = 0.1 M. The standard
cell potential is 0.93 V.
Solution:
° 0.0592 [𝑃𝑏2+] 0.0592 0.1
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑒𝑙𝑙 − 𝑙𝑜𝑔 = 0.93 − 𝑙𝑜𝑔
𝑛 [𝐴𝑔+]2 2 0.752

𝐸𝑐𝑒𝑙𝑙 = 0.93 − −0.02

𝐸𝑐𝑒𝑙𝑙 = 0.95 𝑉

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Equilibrium constant and Cell potential
 When cell attain equilibrium, emf of the cell becomes zero.
 At equilibrium the reaction quotient, Q, becomes equal to equilibrium constant, K
i.e. Q = Keq.
° 2.303𝑅𝑇
 From the Nernst equation, 𝐸 = 𝐸 − log 𝑄
𝑛𝐹
° 0.0592
 Then 0= 𝐸 − log 𝐾
𝑛
° 0.0592
𝐸 = log 𝐾
𝑛
𝑛𝐸 °
log K =
0.0592
−1 𝑛𝐸 °
K = 𝑙𝑜𝑔 ( )
0.0592
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Feasibility of cell reaction
 Since in cell reaction, ∆G = –nFE and ∆G° = –nFE°,
 Gibbs free energy and cell potential may be used to tell about feasibility
(spontaneity) of cell reaction.
 If Ecell is +ve, ∆G would be –ve and cell reaction would be spontaneous
i.e. ∆G = –nF(+E) = –nFE, hence ∆G = –ve ______ spontaneous
 If Ecell is –ve, ∆G would be +ve and cell reaction would be non-
spontaneous.
i.e. ∆G = –nF(– E) = nFE, hence ∆G = +ve ______ non-
spontaneous
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Faraday’s Law of Electrolysis
 The relationship between the quantity of electric charge passed through an electrolyte
and the amount of substance deposited at the electrodes was given by Faraday in 1834,
in the form of the law of electrolysis.
(a) Faraday’s First Law
 “When an electric current is passed through an electrolyte, the amount of substance
deposited is proportional to the quantity of electric charge passed through the
electrolyte”.
If m is the mass of the substance deposited by passing Q coulomb of charge then:
m∝Q
From, Q = I x t Where Z is a constant known as electrochemical
m∝It equivalent and is characteristic of a substance
m=zIt deposited.
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(b) Faraday’s Second Law
• “When the same quantity of electricity is passed through solutions of different
electrolytes, the amounts of the elements deposited is proportional to the chemical
equivalent of the elements”.
OR
• “When the same quantity of charge is passed through different electrolytes, then the
mass of different substance deposited at the respective electrodes will be in the ratio of
their equivalent masses”.
• Mathematically it is represented as;
m1 Z1
=
m2 Z2
Where m1 and m2 are the weight of two substances which are deposited at their respective
electrodes and Z1 and Z2 are their respective equivalent weight (chemical equivalents).

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Homework
1) Given that, Fe2+/ Fe = -0.44 v, Ni+2/ Ni = 0.25 v
Ag+ / Ag = 0.80 v, Cu+2/ Cu = 0.34 v
Which of the following reactions under standard condition will not take place in the
specified direction.
Ni+2(aq) + Cu(s) → Ni(s) + Cu+2(aq)
Cu(s) + 2 Ag+(aq) → Cu+2(aq) + 2 Ag(s)
Cu(s) + 2H+(aq)→ Cu+2 + H2 (g)
Fe(s) + 2H+(aq)→ Fe+2 (aq) + 3 H2
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2) The emf of a cell corresponding to the reaction,
Zn + 2H+ (aq) → Zn+2 (0.1M) + H2(g) 1 atm is 0.30 v at 25 0 C. Write the half cell
reactions and calculate the pH of the solution at the hydrogen electrode. (E0cell = –
0.76 v)
3) The solution of metal of atomic mass X was electrolyzed for 1 hour with a current
of 0.25 ampere. The mass of metal deposited was 0.295g. Find the metal X if its
valency is 2.

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Gravimetric Method of Analysis

 Gravimetric analysis is a method in analytical chemistry to determine the

quantity of an analyte based on the mass of a solid.
 Measuring mass is the most fundamental of all analytical Measurements.
 Gravimetry is unquestionably the oldest analytical technique.
 Therefore, gravimetry is any method in which the signal is mass or
change in mass

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 The steps commonly followed in gravimetric analysis are

1. Preparation of a solution containing a known weight of the sample.

2. Separation of the desired constituent.

3. Weighing the isolated constituent.

4. Computation of the amount of the particular constituent in the

sample from the observed weight of the isolated substance.

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Types of Gravimetric Analysis

• There are four (4) fundamental types of gravimetric analysis.

– Volatilization gravimetry

– Precipitation gravimetry

– Electrogravimetry

– Thermogravimetry

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(i) Volatilization gravimetry
• Volatilisation Gravimetry involves separating components of the mixture by
heating or chemically decomposing the sample.
• Involves collecting and weighing of a volatilized product OR Determining mass
of product from loss in mass of a sample, following volatilization of an analyte or
its decomposition product.
e.g. A sample containing a bicarbonate may be treated with sulphuric acid to evolve
CO2
NaHCO3(aq) + H2SO4(aq) → CO2(g) + H2O(g) + NaHSO4(aq)
• The liberated CO2 be dried to remove H2O and finally retained in weighed tube
that contains an adsorbent (e.g. NaOH) to trap CO2 .

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The difference in mass of the tube before and after adsorption can be used to calculate the
amount of carbonate in the sample.
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 Generally, volatilization involves thermal or chemical decomposition of the
sample and measure the resulting change in its mass.
 Alternatively, a volatile decomposition product can be trapped and weighed
to determine the mass.
 Whether an analysis is direct or indirect, volatilization gravimetry usually
requires to know the products of the decomposition reaction.
 This rarely is a problem for organic compounds, which typically decompose
to form simple gases such as CO2, H2O, and N2.
 For an inorganic compound, however, the products often depend on the
decomposition temperature.

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(ii) Precipitation methods
 Precipitation Gravimetry uses a precipitation reaction to separate one or more
parts of a solution by incorporating it into a solid.
 The analyte is separated from a solution of the sample as a precipitate and is
converted to a compound of known composition that can be weighed.
 For example a sample known to contain Cl¯ as analyte is dissolved in water and
the Cl¯ is converted to a precipitate of AgCl by adding excess AgNO3
Ag+(aq) + Cl–(aq) → AgCl(s)
 The precipitate is washed with water in glass crucible, and dried in an oven It is
cooled and weighed to obtain the weight of AgCl
 Thus chloride content in a sample can be established

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• A gravimetric precipitating agent should react specifically or at least selectively
with the analyte and give precipitates that is:
1. Enough particle size for retaining on filter paper
2. High purity (free of contaminants)
3. Low solubility that no significant loss of the analyte occurs during filtration and
washing
4. Unreactive with air (stable)
5. Known stoichiometric composition after it is dried or, if necessary, ignited
NB:
 Specific reagents: react only with a single chemical species.
 Selective reagents: react with a limited number of species.
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(iii) Thermogravimetry

 Thermogravimetry is a method of thermal analysis in which changes in

physical and chemical properties of materials are measured as a function of
increasing temperature or as a function of time.
 It is done by determining the products of a thermal decomposition through
monitoring the sample’s mass as a function of temperature.
 In thermogravimetry, each change in mass represents the loss of a volatile
product as a result of heating.
 A graphical representation of thermogravimetry is called thermogram.

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• Thermogram for
CaC2O4•H2O obtained
by heating a sample
from room
temperature to
1000°C. Each change
in mass results from
the loss of a volatile
product. The sample’s
initial mass and its
mass after each loss
are shown by the
dotted lines

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 Identifying the products of a thermal decomposition provides
information that we can use to develop an analytical procedure.
For example, the thermogram in previous slide shows that;
– we must heat a precipitate of CaC2O4•H2O to a temperature between
250 and 400oC if we wish to isolate first volatile compound.
– Alternatively, heating the sample to 1000oC allows us to isolate all
volatile compounds and weigh the final solid.

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(iv) Electrogravimetry

 Electrogravimetry is a method used to separate and quantify ions of a

substance, usually a metal.
 In electrogravimetry, the signal is the mass of an electrodeposit on the
cathode or anode in an electrochemical cell by an action of electric
current.
 The principle of electrogravimetry is similar to electroplating; here, the
metal ions are isolated from the solution by depositing on the surface of
the electrode.

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Homework
1) The thermogram for calcium oxalate monohydrate (discussed previously) shows
the mass of a sample of calcium oxalate monohydrate, CaC2O4•H2O, as a function
of temperature. The original sample of 17.61 mg was heated from room
temperature to 1000°C at a rate of 20°C per minute. For each step in the
thermogram, identify the volatilization product and the solid residue that remains.
2) Under the same conditions as in thermogram of CaC2O4•H2O, the thermogram for
a 22.16 mg sample of MgC2O4•H2O shows two steps: a loss of 3.06 mg from 100–
250°C and a loss of 12.24 mg from 350–550°C. For each step, identify the
volatilization product and the solid residue that remains. Using your results from
this exercise and the results from thermogram of CaC2O4•H2O, explain how you
can use thermogravimetry to analyze a mixture that contains CaC2O4•H2O and
MgC2O4•H2O. You may assume that other components in the sample are inert and
thermally stable below 1000°C.

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3) A 101.3 mg sample of an organic compound that contains chlorine is
combusted in pure O2. The volatile gases are collected in absorbent traps
with the trap for CO2 increasing in mass by 167.6 mg and the trap for H2O
increasing in mass by 13.7 mg. A second sample of 121.8 mg is treated with
concentrated HNO3, producing Cl2 that reacts with Ag+ to form 262.7 mg of
AgCl. Determine the compound’s composition, as well as its empirical
formula.
4) A sample of slag from a blast furnace is analyzed for SiO2 by decomposing a
0.5003g sample with HCl, leaving a residue with a mass of 0.1414 g. After
treating with HF and H2SO4, and evaporating the volatile SiF4, a residue with
a mass of 0.0183 g remains. Determine the %w SiO2 in the sample.

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5) Heating a 0.3317g mixture of CaC2O4 and MgC2O4 yields a residue of 0.1794 g
at 600°C and a residue of 0.1294 g at 1000oC. Calculate the %w CaC2O4 in the
sample.
6) A 26.23mg sample of MgC2O4•H2O and inert materials is heated to constant
weight at 1200°C, leaving a residue that weighs 20.98 mg. A sample of pure
MgC2O4•H2O, when treated in the same fashion, undergoes a 69.08% change in
its mass. Determine the %w MgC2O4•H2O in the sample.
7) To determine the amount of magnetite, Fe3O4, in an impure ore, a 1.5419g
sample is dissolved in concentrated HCl, resulting in a mixture of Fe2+and Fe3+.
After adding HNO3 to oxidize Fe2+ to Fe3+ and diluting with water, Fe3+ is
precipitated as Fe(OH)3 using NH3. Filtering, rinsing, and igniting the
precipitate provides 0.8525g of pure Fe2O3. Calculate the %w Fe3O4 in the
sample.
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8) A 0.7336g sample of an alloy that contains copper and zinc is dissolved in 8
M HCl and diluted to 100 mL in a volumetric flask. In one analysis, the zinc
in a 25.00mL portion of the solution is precipitated as ZnNH4PO4, and
isolated as Zn2P2O7, yielding 0.1163 g. The copper in a separate 25.00mL
portion of the solution is treated to precipitate CuSCN, yielding 0.2383 g.
Calculate the %w Zn and the %w Cu in the sample.
9) A 0.611g sample of an alloy that contains Al and Mg is dissolved and treated
to prevent interferences by the alloy’s other constituents. Aluminum and
magnesium are precipitated using 8-hydroxyquinoline, which yields a mixed
precipitate of Al(C9H6NO)3 and Mg(C9H6NO)2 that weighs 7.815 g. Igniting
the precipitate converts it to a mixture of Al2O3 and MgO that weighs 1.002
g. Calculate the %w Al and %w Mg in the alloy.
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10) A sample of a silicate rock that weighs 0.8143g is brought into solution and
treated to yield a 0.2692g mixture of NaCl and KCl. The mixture of
chloride salts is dissolved in a mixture of ethanol and water, and treated
with HClO4, precipitating 0.3314 g of KClO4. What is the %w Na2O in the
silicate rock?
11) An impure sample of Na3PO3 that weighs 0.1392 g is dissolved in 25 mL
of water. A second solution that contains 50 mL of 3% w/v HgCl2, 20 mL of
10% w/v sodium acetate, and 5 mL of glacial acetic acid is prepared.
Adding the solution that contains the sample to the second solution oxidizes
PO33− to PO34− and precipitates Hg2Cl2. After digesting, filtering, and
rinsing the precipitate, 0.4320 g of Hg2Cl2 is obtained. Report the purity of
the original sample as % w/w Na3PO3.

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12) One approach for determining phosphate, PO34−, is to precipitate it as
ammonium phosphomolybdate, (NH4)3PO4•12MoO3. After we isolate the
precipitate by filtration, we dissolve it in acid and precipitate and weigh the
molybdate as PbMoO3. Suppose we know that our sample is at least 12.5%
Na3PO4 and that we need to recover a minimum of 0.600 g of PbMoO3?
What is the minimum amount of sample that we need for each analysis?

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THANKS FOR YOUR ATTENTION

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