Applied Chemistry for Computer Science & Engineering stream 22CHES12/22 Applied Chemistry for Computer Science &

mistry for Computer Science & Engineering stream 22CHES12/22 Applied Chemistry for Computer Science & Engineering stream 22CHES12/22

MODULE 3: CORROSION CHEMISTRY AND ELECTRODE SYSTEM If the medium is alkaline/neutral, Differential aeration corrosion
1
In the presence of dissolved oxygen: 𝐻2 𝑂 + 𝑂2 + 2𝑒 − → 2𝑂𝐻 − 1. When a metal is exposed to different concentration of air (O 2), part of the metal exposed to
2
In the absence of dissolved oxygen:2𝐻2 𝑂 + 2𝑒 − → 2𝑂𝐻 − + 𝐻2 ↑ lower concentration of O2 becomes anodic and undergoes corrosion.
Corrosion Chemistry: Introduction, electrochemical theory of corrosion, types of corrosion-
differential metal and differential aeration. Corrosion control - galvanization, anodization and Example: Rusting of an Iron in the presence of moist air Anodic 2. Other part of the metal exposed to higher concentration of O 2 becomes cathodic and protected
2+ − from thecorrosion.
sacrificial anode method. Corrosion Penetration Rate (CPR) - Introduction and numerical Reaction: 𝐹𝑒 → 𝐹𝑒 + 2𝑒
1 3. The difference in O2 concentration produces a potential difference and causes corrosion. This
problem. Cathodic reaction∶ 𝐻2 𝑂 + 𝑂2 + 2𝑒 − → 2𝑂𝐻 −
2 type of corrosion is called differential aeration corrosion.
Electrode System: Introduction, types of electrodes. Ion selective electrode – definition, Products of anode & cathode: 𝐹𝑒 2+ + 2𝑂𝐻 − → 𝐹𝑒(𝑂𝐻)2
1
construction, working and applications of glass electrode. Determination of pH using glass In the presenceof oxygen: 2𝐹𝑒(𝑂𝐻)2 + 𝑂2 → 𝐹𝑒2 𝑂3 . 2𝐻2 𝑂 Example: 1 Water line corrosion
2
electrode. Reference electrode - Introduction, calomel electrode – construction, working and (Rust) 1) It is observed in steel or iron water tank partially filled with water. Part of the tank just below
applications of calomel electrode. Concentration cell– Definition, construction and Numerical Types of corrosion: water level is exposed to lower concentration of O 2 becomes anodic and undergoescorrosion.
problems. Corrosion can be classified into 2 types as follows 2) Part of the tank above the water line which is exposed to higher concentration of O 2 becomes
cathodic and protected from the corrosion.
Analytical Techniques: Introduction, principle and instrumentation of Conductometry; its 1) Differential metal corrosion (Galvanic corrosion)
3) More corrosion is observed just below the water line; hence this type is called water line
application in the estimation of weak acid. Potentiometry; its application in the estimation of 2) Differential aeration corrosion
corrosion.
iron.
Differential metal corrosion (Galvanic corrosion) Reactions:
CORROSION CHEMISTRY 1) When two dissimilar metals are in direct contact with one another and exposed to a corrosive
medium, the metal with lower electrode potential becomes anode and suffers from corrosion,
The term corrosion is used to denote a change. A metal changes from its elementary state to the whereas the metal with higher electrode potential becomes cathode and protected from
corrosion. This type of corrosion is known as differential metal corrosion or galvanic
combined state when it comes in contact with liquid medium. This is actually due to the
chemical interaction between the metal and the environment. corrosion.
2) The rate of corrosion depends mainly on the difference in the position of the two metals in
Definition: “The spontaneous deterioration and consequent loss of a metal/alloy due to galvanicseries.
chemical/electrochemical attack by the environment”. 3) Higher the difference, faster is the rate ofcorrosion.
Example: When iron metal is exposed to the moist environment, the metal forms a hydrated Example: Electrode potential of iron (-0.44 V) is less than that of copper (0.34 V). Therefore
ferric oxide called rust which is relatively non-protective. when iron is in contact with copper, iron becomes anodic and undergoes corrosion, whereas
copper becomes cathodic and protected from the corrosion. 𝐴𝑡 𝐴𝑛𝑜𝑑𝑒: 𝐹𝑒 → 𝐹𝑒 2+ + 2𝑒 −
Most of the corrosion cases are electrochemical in nature taking place by an electrochemical
attack on the metal in the presence of air and moisture (H2O) called wet corrosion. The 𝐴𝑡 𝐴𝑛𝑜𝑑𝑒: 𝐹𝑒 → 𝐹𝑒 2+ + 2𝑒 − 1
𝐴𝑡 𝐶𝑎𝑡ℎ𝑜𝑑𝑒 ∶ 𝐻2 𝑂 + 𝑂2 + 2𝑒 − → 2𝑂𝐻 −
mechanism of the wet corrosion is explained on the basis of electrochemical theory of corrosion. 2
1 𝐹𝑒 2+ + 2𝑂𝐻 − → 𝐹𝑒(𝑂𝐻)2 ,
Electrochemical theory of corrosion: 𝐴𝑡 𝐶𝑎𝑡ℎ𝑜𝑑𝑒 ∶ 𝐻2 𝑂 + 𝑂2 + 2𝑒 − → 2𝑂𝐻 − 1
2
2𝐹𝑒(𝑂𝐻)2 + 𝑂2 → 𝐹𝑒2 𝑂3 . 2𝐻2 𝑂
According to this theory, 𝐹𝑒 2+ + 2𝑂𝐻 − → 𝐹𝑒(𝑂𝐻)2 2
Example: 2 pitting corrosion
1. When a metal is in contact with moist air or when dissimilar metals are contact with each 1
2𝐹𝑒(𝑂𝐻)2 + 2 𝑂2 → 𝐹𝑒2 𝑂3 . 2𝐻2 𝑂 1) Pitting corrosion is observed when dust particles get deposited over the metalsurface.
other in a solution, large numbers of galvanic cells are formed with the existence of anodic 2) The portion of the metal covered by dust which is less aerated becomes anodic and suffers
and cathodic area on the metal. fromcorrosion.
2. In this corrosion, oxidation of the metal and reduction of species present in solution takes 3) Thus, metal is lost below the surface of dust particle forming a deep and narrowpit.
place. 4) The adjacent area of the metal which is exposed to higher concentration of O2 becomes
3. The anodic part of the metal undergo oxidation and suffers from corrosion, cathodic part cathodic and protected fromcorrosion.
undergo reduction and protected fromcorrosion.
4. The electrons are transferred through the metal from anode to cathode.
5. During corrosion the following reactions takesplace.
At anode (oxidation reaction) : 𝑀 → 𝑀𝑛+ + 𝑛𝑒 −
The reaction at cathode (reduction reaction) depends on the nature of the environment: If the
medium is acidic,
1
In the presence ofdissolved oxygen: 2𝐻 + 2 𝑂2 + 2𝑒 − → 𝐻2 𝑂
+

In the absence ofdissolvedoxygen: 2𝐻+ + 2𝑒 − → 𝐻2

Department of Chemistry, SVIT Page 1 Department of Chemistry, SVIT Page 2 Department of Chemistry, SVIT Page 3

Applied Chemistry for Computer Science & Engineering stream 22CHES12/22 Applied Chemistry for Computer Science & Engineering stream 22CHES12/22 Applied Chemistry for Computer Science & Engineering stream 22CHES12/22
Sacrificial anodic protection: ELECTRODE SYSTEM
Reactions:
𝐴𝑡 𝐴𝑛𝑜𝑑𝑒: 𝐹𝑒 → 𝐹𝑒 2+ + 2𝑒 − 1) The metal to be protected is connected to a more anodic metal using a metallicwire. Types of electrodes:
1 2) The more active metal gets corroded while the parent structure is protected fromcorrosion. 1) Metal-metal ion exchange: In this electrode, a metal is immersed in the ionic solution of its
𝐴𝑡 𝐶𝑎𝑡ℎ𝑜𝑑𝑒 ∶ 𝐻2 𝑂 + 𝑂2 + 2𝑒 − → 2𝑂𝐻 −
2 3) The more active metal so employed is called sacrificialanode. own salts. Example: Cu/Cu2+
𝐹𝑒 2+ + 2𝑂𝐻 − → 𝐹𝑒(𝑂𝐻)2 4) The sacrificial anodes to be replaced by fresh ones as and when it isrequired. 2) Redox electrode: In this electrode, ions of a chemical species in two different oxidation states
1 5) Commonly used sacrificial anodes are: Mg, Zn, Aletc. are in contact with each other. Example: Pt
2𝐹𝑒(𝑂𝐻)2 + 𝑂2 → 𝐹𝑒2 𝑂3 . 2𝐻2 𝑂
2 Example: steel pipe is protected by connecting it to a block of Zn. In such cases steel acts as a 3) Gas Electrode: In this electrode, an inert metal like platinum is in contact with gas molecules
Corrosion Control: cathode and is unaffected or protected from corrosion and Zn act as anode and undergoes Examples: Standard Hydrogen electrode
Galvanization sacrificial corrosion. 4) Metal-Insoluble salt electrode: In this electrode, metal is in contact with its insoluble salt.
Example: Calomel Electrode
Coating of zinc on iron or steel by hot dipping process is called galvanizing. (M.P of Zn=419 °C) 5) Amalgum electrode: In this electrode, a known concentration of metal dissolved in liquid
It is carried out as follows, mercury is in contact with ionic solution of the metal. Example: Pb(Hg)
6) Ion selective electrode: This electrode is more selective towards a particular type of ion in the
mixture. Example: Glass electrode

Ion-selective electrode
The electrode, which are responds to a specific ion in a mixture by ignoring other ions are called
as ion selective electrodes. They consist of a thin membrane in contact with ion solution.
Example, glasselectrode
Corrosion Penetration Rate (CPR)
Glass Electrode:
1) The iron sheet is subjected to pretreatment by degreasing with organicsolvent. The corrosion penetration rate (CPR) is defined as “the speed at which any metal in a specific
This electrode works on the principle that when a thin, low resistivity glass membrane is in
environment deteriorates due to chemical reactions when it is exposed to a corrosive
2) The sheet is passed through dilute H2SO4 to remove anyrust. contact with a solution containing H+ions, a potential develops across the membrane and the
3) Washed with distilled water and dried by supplying hotair. environment” or the amount of corrosion loss per unit time in thickness or the speed at which
solution. Potential developed depends on the concentration of hydrogen ions in thesolution.
4) Then iron sheet is dipped in molten bath of Zn at 419°C and surface is covered with NH4Cl corrosion spreads to the inner portions of a material. Corrosion rate depends on the metal and the
flux which prevents the oxidation of Zn metal. environmental condition.
Construction:
The CPR is given by
5) The excess of coated metal is removed by passing through a pair of hot rollers and cooled
k×W  It consists of a long glass tube with a thin-walled glass bulb containing 0.1 M HCl [C1].
gradually. CPR = Ag/AgCl electrode placed inside the solution to provide electrical contact.
D×A×T
Where k = a constant  The glass electrode is dipped in unknown solution of concentration C 2.
Anodizing  Thepotential developed across the membraneby the exchange of ions with the composition of
W = total weight lost
Anodizing is the process of oxidation of outer layer of metal to its metal oxide by electrolysis.
T = time taken for the loss of metal glass is known as the boundary potential Eb (E2– E1).
Oxide layer formed over the metal itself acts as protective layer.
A = the surface area of the exposed metal  Even when C1 =C2 , E≠ 0 a small potential is developed across the membrane, it is calledas
Anode : Aluminium asymmetric potential (Easy).
D = the metal density in g/cm³
Cathode : Steel orCopper
Electrolyte : 5-10% chromicacid
The corrosion penetration rate is expressed in terms of thickness or weight loss when the surface
Temperature : 30-40 °C
of the metal corrodes uniformly across an area.
Appliedpotential : 0-40V
This method involves the exposure of a weighed piece of test metal or alloy to a specific
Aluminum is made as anode and copper or steel is used as cathode. The electrodes are immersed
environment for a specific time. This is followed by a thorough cleaning to remove the corrosion
in an electrolyte consisting of 5-10% chromic acid. The temperature is maintained at 30-40 °C.
products and then determining the weight of the metal after corrosion.
Potential of 0-40 V is applied which oxidizes outer layer of Al to Al2O3 and that get deposited
The rate may vary if the rate expressed by the formula above is used to compare corrosion rates
over the metal. The reactions involved are as follows
for a period longer than one year with rates calculated over short periods. This is because the short
time periods are prone to fluctuating environmental changes from season to season and from day
𝐴𝑡 𝐴𝑛𝑜𝑑𝑒: 2𝐴𝑙(𝑠) + 3𝐻2 𝑂(𝑙) → 𝐴𝑙2 𝑂3 (𝑠) + 6𝐻 + + 6𝑒 − to day.
𝐴𝑡 𝐶𝑎𝑡ℎ𝑜𝑑𝑒: 6𝐻 + + 6𝑒 − → 3𝐻2 (𝑔) Note:-
𝑂𝑣𝑒𝑟 𝑎𝑙𝑙 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛: 2𝐴𝑙(𝑠) + 3𝐻2 𝑂(𝑙) → 𝐴𝑙2 𝑂3 (𝑠) + 3𝐻2 (𝑔) Unit of CPR is mils per year if W is in mg, A in Inch2, D in g/cm3, t in hrs and k value will be
534. (1mil = 0.001 inch)
The anodized coatings are thicker than the natural oxide film and possess improved corrosion Unit of CPR is mm per year if W is in mg, A in cm2, D in g/cm3, t in hrs and k value will be 87.6.
resistance as well as resistance to mechanical injury. (1inch = 2.54 cm)
If CRP is less than 20m/year or 0.5 mm/year, it is acceptable for most of the application.

Department of Chemistry, SVIT Page 4 Department of Chemistry, SVIT Page 5 Department of Chemistry, SVIT Page 6

Applied Chemistry for Computer Science & Engineering stream 22CHES12/22 Applied Chemistry for Computer Science & Engineering stream 22CHES12/22 Applied Chemistry for Computer Science & Engineering stream 22CHES12/22
Cell representation: Ag / AgCl / HCl (0.1M) / unknown solution/ Glass The emf of a cell is determined by using voltmeter. Applying Nernst equation,
Ecell is the difference b/w glass electrode potential E G and the calomel electrode potential E SCE. 0.0591 [𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠]
Working: 𝐸𝐶𝑒𝑙𝑙 = 𝐸𝐶𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝐴𝑛𝑜𝑑𝑒 𝐸 = 𝐸0 + 𝑙𝑜𝑔
𝑛 [𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠]
E1& E2 is the potential developed at outer and inner membrane respectively the boundary 𝐸𝐶𝑒𝑙𝑙 = 𝐸𝐺 − 𝐸𝑆𝐶𝐸
0.0591 [𝐻𝑔2 𝐶𝑙2 ]
potential is, 𝐸𝑏 = 𝐸2 − 𝐸1 𝐸𝐶𝑒𝑙𝑙 = 𝐿1 − 0.0591𝑝𝐻 − 𝐸𝑆𝐶𝐸 𝐸 = 𝐸0 + 𝑙𝑜𝑔
0.0591 0.0591 𝑛 [𝐻𝑔]2 [𝐶𝑙]2−
𝐸𝑏 = 𝐸 0 + log[𝐶2] − {𝐸 0 + log[𝐶1]} 𝐾 − 𝐸𝐶𝑒𝑙𝑙
𝑛 𝑛 𝑝𝐻 = [𝐾 = 𝐿1 − 𝐸𝑆𝐶𝐸 ] Since [Hg2Cl2] = [Hg] 2 = 1, the above equation becomes
0.0591
0.0591 0.0591
𝐸𝑏 = log[𝐶2] − log[𝐶1] Where K= Electrode assembly constant. 0.0591 1
𝑛 𝑛 𝐸 = 𝐸0 + log −
2 [𝐶𝑙 ]
0.0591 0.0591 1 Reference electrodes
𝐸𝑏 = log[𝐶2] + 𝑙𝑜𝑔 The calomel electrode potential is depending on the concentration of chloride ions in KCl. If the
𝑛 𝑛 [𝐶1] Reference electrodes are the electrodes whose potential is known and used for determination of Concentration of chloride ions increases, the potential decreases and vice versa. (The potential of
0.0591 1 potential of unknown electrodes
Where 𝐿= 𝑛
𝑙𝑜𝑔 [𝐶1] calomel is inversely proportional to the concentration of chloride ions)
Calomel Electrode: The potential of calomel electrode is measured with respect to SHE and it depends on
Therefore concentration of KCl solution used.
0.0591 Construction:
𝐸𝑏 = 𝐿 + log[𝐶2]
𝑛 Conc. KCl 0.1N 1N Saturated KCl
Here n=1, [C2] = [H+] ions in outer membrane, Then 1) Calomel electrode consists of long glass tube with two side tubes.
2) One at the top to fill saturated KCl solution and the other side tube is connected to the salt Potential (V) 0.334V 0.281V 0.242V
𝐸𝑏 = 𝐿 + 0.0591log[𝐻+ ] bridge. Mercury is placed at the bottom which is covered with a layer of Hg and Hg 2Cl2
(calomel) paste. Applications:
𝐸𝑏 = 𝐿 − 0.0591𝑝𝐻 (pH= -log[H+] )
3) The remaining portion is filled with saturated KCl solution. 1) Used to determine the potential of the otherelectrodes.
The Glass electrode potential is given by 4) A platinum wire is dipped into the mercury and is used to provide external electrical contact. 2) It is commonly used as reference electrode in all potentiometricdeterminations.
 The calomel electrode is representedas,Cl-/Hg2Cl2/Hg
𝐸𝐺 = 𝐸𝑏 + 𝐸𝐴𝑔/𝐴𝑔𝐶𝑙 + 𝐸𝐴𝑠𝑦
Electrolytic Concentration Cell:
Substitute the value of Eb It is galvanic cell, which consists of two identical electrodes, which are in contact with the same
𝐸𝐺 = 𝐿 − 0.0591𝑝𝐻 + 𝐸𝐴𝑔/𝐴𝑔𝐶𝑙 + 𝐸𝐴𝑠𝑦 solution of electrolyte in different concentrations.
Example:
Consider𝐿1 = 𝐿 + 𝐸𝐴𝑔/𝐴𝑔𝐶𝑙 + 𝐸𝐴𝑠𝑦 , Therefore Consider two silver electrodes that in contact with the AgNO3 solution of different
concentrations (M1 and M2) connected through voltmeter. The electrolytes are connected through
𝐸𝐺 = 𝐿1 − 0.0591𝑝𝐻 salt bridge.
Determination of pH of a solution using Glass Electrode The cell representation Ag/ AgNO3 (M1)// AgNO3 (M2)/Ag

The potential of a glass electrode depends on the concentration of H + ions. Hence, pH of a Where M1 and M2 are the molar concentration of the Ag+ ions in the two half-cells.
solution can be determined by using glass electrode and calomel electrode assembly.
The cell assembly is represented as
Hg/Hg2Cl2/Cl- // solution of unknown pH / glass/0.1 M HCl / AgCl / Ag

Working:

Calomel electrode behaves as anode or cathode depending upon the nature of another electrode.
The half-cell reaction when it acts as an anode is
2𝐻𝑔 + 2𝐶𝑙 − → 𝐻𝑔2 𝐶𝑙2 + 2𝑒 −

The half-cell reaction when it acts as a cathode is

𝐻𝑔2 𝐶𝑙2 + 2𝑒 − → 2𝐻𝑔 + 2𝐶𝑙 −

Department of Chemistry, SVIT Page 7 Department of Chemistry, SVIT Page 8 Department of Chemistry, SVIT Page 9

Applied Chemistry for Computer Science & Engineering stream 22CHES12/22 Applied Chemistry for Computer Science & Engineering stream 22CHES12/22 Applied Chemistry for Computer Science & Engineering stream 22CHES12/22

𝐴𝑡 𝐴𝑛𝑜𝑑𝑒: 𝐴𝑔 → 𝐴𝑔+ (𝑀1) + 𝑒 − Types of conductance: There are three type’s namely specific conductance, equivalence
𝐴𝑡 𝐶𝑎𝑡ℎ𝑜𝑑𝑒: 𝐴𝑔+ (𝑀2) + 𝑒 − → 𝐴𝑔 Applications conductance, and molar conductance.
𝑁𝑒𝑡 𝐶𝑒𝑙𝑙 𝑅𝑒𝑎𝑐𝑡𝑖𝑜𝑛: 𝐴𝑔+ (𝑀2) ↔ 𝐴𝑔+ (𝑀1) 1. Estimation of concentration of the ionic species present in the givensolution. Specific conductance (K) is the conductance of the solution present between two parallel
2. Coloured solution can also betitrated electrodes of 1cm2 area of cross section and 1cm apart.
Apply Nernst equation for the cell reaction, 3. Acid-base titration can also be done in thismethod. K = 1/R (l/a) K = Siemen m-1
4. In this method Oxidation-reduction titrations can also be carriedout. Equivalence conductance (λ) is the conductance of the solution when 1g equivalent weight of
0.0591 [𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠] 5. Precipitation reactions can also be carried outpotentiometrically. solution is placed between two electrodes of area 1cm2 at 1cm apart.
𝐸 = 𝐸0 + 𝑙𝑜𝑔 Molar conductance (µ) is the conductance of the solution when 1g molecular weight of solute is
𝑛 [𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠]
For example: placed between two electrodes of area 1cm2 at 1cm apart
Procedure: Pipette out 25cm3 of FAS solution into a 50 cm3 Application of Conductometric titration
𝐸 0 = 𝐸 0 𝐶𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸 0𝐴𝑛𝑜𝑑𝑒
beaker. Add one test tube full of dil H2SO4. Immerse Pt. & It is used in the estimation of acids and bases present in the sample solutions. The possible
calomel electrodes into the solution, & connect the electrodes to combinations and conductance responses are explained below,
Since both anode & cathode is made up of same metal, 𝐸 0 = 0
a potentiometer. Fill the burette with K2Cr2O7 solution. Add Strong acid v/s strong base (HCl v/s NaOH)
0.0591 [𝑀2] 0.0591 [𝑀2] K2Cr2O7 solution from the burette with increment of 0.5cm3, If the strong acid like HCl is titrated against a strong base such as NaOH, the conductance first
𝐸 =0+ 𝑙𝑜𝑔 𝑜𝑟 𝐸 = 𝑙𝑜𝑔 stir well and measure the potential after each addition. Continue decreases due to replacement
𝑛 [𝑀1] 𝑛 [𝑀1]
the titration till the potential indicates a rapid jump with a drop of fast moving 𝐻 + ions by slow moving Na+ ions
[Link] the graph of ∆E/ ∆V v/s vol. of K2Cr2 O7. HCl + NaOH → NaCl + H2 O
ANALYTICAL TECHNIQUES
After the neutralization point, conductivity rapidly rises with further addition of NaOH because
Potentiometric Titration
Conductometric Titration of continuous addition of fast moving OH- ions. A plot of conductance against the volume of
Aim: Determination of the weight of ferrous ammonium sulphate and ferrous iron in the given base added is shown in the figure. The point of intersection of two curves gives the neutralization
solution by potentiometric titration method. Conductance is ease with which current flows through the solution. It is reciprocal of resistance. point.
C=1/R = Ω-1 or mho or siemen
Theory: In this titration the amount of substance in the solution is determined by measuring the
emf between two electrodes that are dipped into the solution. When the metal M is immersed in Theory:
the solution containing its own ions M n+ ions, the electrode potential is given by Nernst equation, The Conductance of the solution is explained by considering ohm’s law.
0.0591
𝐸 = 𝐸 0 + 𝑛 𝑙𝑜𝑔[𝑀𝑛+ ] According to ohm’s law the current flowing through the conductor is directly proportional to
From this equation the potential of the electrode is directly proportional to the concentration of voltageand inversely proportional to the resistance.
the ionic species present in the solution. I= or E=IR
The resistance of the any conductor is directly proportional to the length, inverselyproportional
Instrumentation: to the area of cross section of the conductor Therefore R = S (l/a) where S is specific resistance
A potentiometer consists of a indicator electrode (e.g.: Platinum) and an saturated reference Therefore C = 1/R =1/S(a/l), K(a/l), K = specificconductance
electrode (E.g.: Calomel electrode), stirrer & potentiometer to measure the potential values. It is defined as the conductance of the solution present between two parallel electrodes of 1cm2 Weak acid v/s Strong base (CH3COOH v/s NaOH)
Emf of the solution can be measured by combining reference electrode with indicator electrode. area of cross section and 1cm apart. Consider the titration of acetic acid against NaOH. The conductance of the acid will be initially
The electrode which responds to the change in the concentration of the ion in the solution is The conductance of the solution is depending on mobility of the ion and number of the ion. low since acetic acid is a weak electrolyte. When NaOH is added to the acid, the salt formed is
called indicator electrode & reference electrode is one whose potential is constant. A known highly ionized and the conductance increases. On complete neutralization of the acid, further
volume of the analyte is taken in beaker and its potential is measured. The titrant is added in Instrumentation: addition of base leads to an increase in the number of mobile OH- ions. Hence the conductance
increments of 0.5ml and potential is measured each time. Near the equivalence point there is a It consists of two platinum electrodes each of unit area of cross section placed at unit distance increases sharply.
sharp increase in the potential. The end point is determined by plotting change in potential apart. The electrodes are dipped in the electrolytic solution taken in a beaker. It is connected to a CH3 COOH + NaOH → CH3 COONa + H2 O
against volume of the titrant. conductometer to measure the conductance. The conductance is measured after the addition of
the titrant at interval of 0.5 ml. A plot of conductance against the volume of base added is shown in the figure. The point of
intersection of two curves gives the neutralization point.

Department of Chemistry, SVIT Page 10 Department of Chemistry, SVIT Page 11 Department of Chemistry, SVIT Page 12
Applied Chemistry for Computer Science & Engineering stream 22CHES12/22

Mixture of strong acid and weak acid v/s strong base (HCl & CH3COOH v/s NaOH)
The strong acid like HCl is titrated against a strong base such as NaOH, the conductance firs
decreases due to replacement of fast-moving H+ ions by slow moving Na+ ions

HCl + NaOH NaCl +H2O

The weak acid does not get neutralized initially because of the well-known common ion effect.
In the presence of excess of H+ ions, the ionization of the weak acid is suppressed and hence,
weak acid like CH3COOH ionizes gradually after the first end point and the available H + ions are
neutralized giving the second end point. Because of common ion effect dissolution of acetic acid
is suppressed. Hence it does not provide H+ ions which required for neutralization.
After the neutralization point of HCl, CH3COOH, conductivity rapidly rises with further addition
of NaOH because of continuous addition of fast moving OH - ions. A plot of conductance against
the volume of base added is shown in the figure. The point of intersection of two curves gives
the neutralization point.

*****************************************************************************

Department of Chemistry, SVIT Page 13