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MODULE 3: CORROSION CHEMISTRY AND ELECTRODE SYSTEM If the medium is alkaline/neutral, Differential aeration corrosion
1 Reactions:
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. 𝐴𝑡 𝐴𝑛𝑜𝑑𝑒: 𝐹𝑒 → 𝐹𝑒 2+ + 2𝑒 −
Corrosion Chemistry: Introduction, electrochemical theory of corrosion, types of corrosion- 1
2. Other part of the metal exposed to higher concentration of O 2 becomes cathodic and protected
differential metal and differential aeration. Corrosion control - galvanization, anodization and Example: Rusting of an Iron in the presence of moist air Anodic 𝐴𝑡 𝐶𝑎𝑡ℎ𝑜𝑑𝑒 ∶ 𝐻2 𝑂 + 𝑂2 + 2𝑒 − → 2𝑂𝐻 −
sacrificial anode method. Corrosion Penetration Rate (CPR) - Introduction and numerical Reaction: 𝐹𝑒 → 𝐹𝑒 2+ + 2𝑒 − from thecorrosion. 2
1 3. The difference in O2 concentration produces a potential difference and causes corrosion. This 𝐹𝑒 2+ + 2𝑂𝐻 − → 𝐹𝑒(𝑂𝐻)2
problem. Cathodic reaction∶ 𝐻2 𝑂 + 2 𝑂2 + 2𝑒 − → 2𝑂𝐻 − 1
type of corrosion is called differential aeration corrosion.
Products of anode & cathode: 𝐹𝑒 2+ + 2𝑂𝐻 − → 𝐹𝑒(𝑂𝐻)2 2𝐹𝑒(𝑂𝐻)2 + 𝑂2 → 𝐹𝑒2 𝑂3 . 2𝐻2 𝑂
Electrode System: Introduction, types of electrodes. Ion selective electrode – definition, 2
1 Corrosion Control:
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 Galvanization
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 Coating of zinc on iron or steel by hot dipping process is called galvanizing. (M.P of Zn=419 °C)
cathodic and protected from the corrosion. It is carried out as follows,
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
corrosion.
chemical interaction between the metal and the environment.
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. 1) The iron sheet is subjected to pretreatment by degreasing with organicsolvent.
chemical/electrochemical attack by the environment”. 3) Higher the difference, faster is the rate ofcorrosion. 2) The sheet is passed through dilute H2SO4 to remove anyrust.
3) Washed with distilled water and dried by supplying hotair.
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 4) Then iron sheet is dipped in molten bath of Zn at 419°C and surface is covered with NH4Cl
ferric oxide called rust which is relatively non-protective. when iron is in contact with copper, iron becomes anodic and undergoes corrosion, whereas flux which prevents the oxidation of Zn metal.
copper becomes cathodic and protected from the corrosion. 𝐴𝑡 𝐴𝑛𝑜𝑑𝑒: 𝐹𝑒 → 𝐹𝑒 2+ + 2𝑒 − 5) The excess of coated metal is removed by passing through a pair of hot rollers and cooled
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 gradually.
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 , Anodizing
Electrochemical theory of corrosion: 𝐴𝑡 𝐶𝑎𝑡ℎ𝑜𝑑𝑒 ∶ 𝐻2 𝑂 + 𝑂2 + 2𝑒 − → 2𝑂𝐻 − 1
2 Anodizing is the process of oxidation of outer layer of metal to its metal oxide by electrolysis.
2𝐹𝑒(𝑂𝐻)2 + 𝑂2 → 𝐹𝑒2 𝑂3 . 2𝐻2 𝑂 Oxide layer formed over the metal itself acts as protective layer.
According to this theory, 𝐹𝑒 2+ + 2𝑂𝐻 − → 𝐹𝑒(𝑂𝐻)2 2
Example: 2 pitting corrosion Anode : Aluminium
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. Cathode : Steel orCopper
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 Electrolyte : 5-10% chromicacid
and cathodic area on the metal. fromcorrosion. Temperature : 30-40 °C
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. Appliedpotential : 0-40V
place. 4) The adjacent area of the metal which is exposed to higher concentration of O2 becomes Aluminum is made as anode and copper or steel is used as cathode. The electrodes are immersed
3. The anodic part of the metal undergo oxidation and suffers from corrosion, cathodic part cathodic and protected fromcorrosion. in an electrolyte consisting of 5-10% chromic acid. The temperature is maintained at 30-40 °C.
undergo reduction and protected fromcorrosion. Potential of 0-40 V is applied which oxidizes outer layer of Al to Al2O3 and that get deposited
4. The electrons are transferred through the metal from anode to cathode. over the metal. The reactions involved are as follows
5. During corrosion the following reactions takesplace.
At anode (oxidation reaction) : 𝑀 → 𝑀𝑛+ + 𝑛𝑒 − 𝐴𝑡 𝐴𝑛𝑜𝑑𝑒: 2𝐴𝑙(𝑠) + 3𝐻2 𝑂(𝑙) → 𝐴𝑙2 𝑂3 (𝑠) + 6𝐻 + + 6𝑒 −
The reaction at cathode (reduction reaction) depends on the nature of the environment: If the 𝐴𝑡 𝐶𝑎𝑡ℎ𝑜𝑑𝑒: 6𝐻 + + 6𝑒 − → 3𝐻2 (𝑔)
medium is acidic, 𝑂𝑣𝑒𝑟 𝑎𝑙𝑙 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛: 2𝐴𝑙(𝑠) + 3𝐻2 𝑂(𝑙) → 𝐴𝑙2 𝑂3 (𝑠) + 3𝐻2 (𝑔)
1
In the presence ofdissolved oxygen: 2𝐻+ + 2 𝑂2 + 2𝑒 − → 𝐻2 𝑂
The anodized coatings are thicker than the natural oxide film and possess improved corrosion
In the absence ofdissolvedoxygen: 2𝐻+ + 2𝑒 − → 𝐻2
resistance as well as resistance to mechanical injury.

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Sacrificial anodic protection: ELECTRODE SYSTEM Cell representation: Ag / AgCl / HCl (0.1M) / unknown solution/ Glass The emf of a cell is determined by using voltmeter.
Ecell is the difference b/w glass electrode potential E G and the calomel electrode potential E SCE.
1) The metal to be protected is connected to a more anodic metal using a metallicwire. Types of electrodes: Working: 𝐸𝐶𝑒𝑙𝑙 = 𝐸𝐶𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝐴𝑛𝑜𝑑𝑒
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 E1& E2 is the potential developed at outer and inner membrane respectively the boundary 𝐸𝐶𝑒𝑙𝑙 = 𝐸𝐺 − 𝐸𝑆𝐶𝐸
3) The more active metal so employed is called sacrificialanode. own salts. Example: Cu/Cu2+ potential is, 𝐸𝑏 = 𝐸2 − 𝐸1 𝐸𝐶𝑒𝑙𝑙 = 𝐿1 − 0.0591𝑝𝐻 − 𝐸𝑆𝐶𝐸
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 0.0591 0.0591
5) Commonly used sacrificial anodes are: Mg, Zn, Aletc. are in contact with each other. Example: Pt 𝐸𝑏 = 𝐸 0 + log[𝐶2] − {𝐸 0 + log[𝐶1]} 𝐾 − 𝐸𝐶𝑒𝑙𝑙
𝑛 𝑛 𝑝𝐻 = [𝐾 = 𝐿1 − 𝐸𝑆𝐶𝐸 ]
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 0.0591
cathode and is unaffected or protected from corrosion and Zn act as anode and undergoes 0.0591 0.0591
Examples: Standard Hydrogen electrode 𝐸𝑏 = log[𝐶2] − log[𝐶1] Where K= Electrode assembly constant.
sacrificial corrosion. 4) Metal-Insoluble salt electrode: In this electrode, metal is in contact with its insoluble salt. 𝑛 𝑛
Example: Calomel Electrode 0.0591 0.0591 1 Reference electrodes
5) Amalgum electrode: In this electrode, a known concentration of metal dissolved in liquid 𝐸𝑏 = log[𝐶2] + 𝑙𝑜𝑔
𝑛 𝑛 [𝐶1] Reference electrodes are the electrodes whose potential is known and used for determination of
mercury is in contact with ionic solution of the metal. Example: Pb(Hg)
0.0591 1 potential of unknown electrodes
6) Ion selective electrode: This electrode is more selective towards a particular type of ion in the Where 𝐿= 𝑙𝑜𝑔 [𝐶1]
𝑛
mixture. Example: Glass electrode Calomel Electrode:
Therefore
Ion-selective electrode 0.0591 Construction:
𝐸𝑏 = 𝐿 + log[𝐶2]
The electrode, which are responds to a specific ion in a mixture by ignoring other ions are called 𝑛 1) Calomel electrode consists of long glass tube with two side tubes.
as ion selective electrodes. They consist of a thin membrane in contact with ion solution. Here n=1, [C2] = [H+] ions in outer membrane, Then
2) One at the top to fill saturated KCl solution and the other side tube is connected to the salt
Example, glasselectrode 𝐸𝑏 = 𝐿 + 0.0591log[𝐻+ ] bridge. Mercury is placed at the bottom which is covered with a layer of Hg and Hg 2Cl2
Corrosion Penetration Rate (CPR)
(calomel) paste.
Glass Electrode: 𝐸𝑏 = 𝐿 − 0.0591𝑝𝐻 (pH= -log[H+] )
The corrosion penetration rate (CPR) is defined as “the speed at which any metal in a specific 3) The remaining portion is filled with saturated KCl solution.
This electrode works on the principle that when a thin, low resistivity glass membrane is in The Glass electrode potential is given by 4) A platinum wire is dipped into the mercury and is used to provide external electrical contact.
environment deteriorates due to chemical reactions when it is exposed to a corrosive
contact with a solution containing H+ions, a potential develops across the membrane and the  The calomel electrode is representedas,Cl-/Hg2Cl2/Hg
environment” or the amount of corrosion loss per unit time in thickness or the speed at which 𝐸𝐺 = 𝐸𝑏 + 𝐸𝐴𝑔/𝐴𝑔𝐶𝑙 + 𝐸𝐴𝑠𝑦
solution. Potential developed depends on the concentration of hydrogen ions in thesolution.
corrosion spreads to the inner portions of a material. Corrosion rate depends on the metal and the
environmental condition. Substitute the value of Eb
Construction:
The CPR is given by
 It consists of a long glass tube with a thin-walled glass bulb containing 0.1 M HCl [C1]. 𝐸𝐺 = 𝐿 − 0.0591𝑝𝐻 + 𝐸𝐴𝑔/𝐴𝑔𝐶𝑙 + 𝐸𝐴𝑠𝑦
k×W
CPR = Ag/AgCl electrode placed inside the solution to provide electrical contact.
D×A×T Consider𝐿1 = 𝐿 + 𝐸𝐴𝑔/𝐴𝑔𝐶𝑙 + 𝐸𝐴𝑠𝑦 , Therefore
Where k = a constant  The glass electrode is dipped in unknown solution of concentration C 2.
W = total weight lost  Thepotential developed across the membraneby the exchange of ions with the composition of 𝐸𝐺 = 𝐿1 − 0.0591𝑝𝐻
T = time taken for the loss of metal glass is known as the boundary potential Eb (E2– E1).
 Even when C1 =C2 , E≠ 0 a small potential is developed across the membrane, it is calledas Determination of pH of a solution using Glass Electrode
A = the surface area of the exposed metal
D = the metal density in g/cm³ asymmetric potential (Easy). The potential of a glass electrode depends on the concentration of H + ions. Hence, pH of a
solution can be determined by using glass electrode and calomel electrode assembly.
The corrosion penetration rate is expressed in terms of thickness or weight loss when the surface The cell assembly is represented as
of the metal corrodes uniformly across an area. Hg/Hg2Cl2/Cl- // solution of unknown pH / glass/0.1 M HCl / AgCl / Ag
This method involves the exposure of a weighed piece of test metal or alloy to a specific
environment for a specific time. This is followed by a thorough cleaning to remove the corrosion Working:
products and then determining the weight of the metal after corrosion.
The rate may vary if the rate expressed by the formula above is used to compare corrosion rates
Calomel electrode behaves as anode or cathode depending upon the nature of another electrode.
for a period longer than one year with rates calculated over short periods. This is because the short
The half-cell reaction when it acts as an anode is
time periods are prone to fluctuating environmental changes from season to season and from day
2𝐻𝑔 + 2𝐶𝑙 − → 𝐻𝑔2 𝐶𝑙2 + 2𝑒 −
to day.
Note:- The half-cell reaction when it acts as a cathode is
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)
𝐻𝑔2 𝐶𝑙2 + 2𝑒 − → 2𝐻𝑔 + 2𝐶𝑙 −
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.
The electrode reaction is,
(1inch = 2.54 cm)
𝐻𝑔2 𝐶𝑙2 + 2𝑒 − ↔ 2𝐻𝑔 + 2𝐶𝑙 −
If CRP is less than 20m/year or 0.5 mm/year, it is acceptable for most of the application.

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Applying Nernst equation, 𝐴𝑡 𝐴𝑛𝑜𝑑𝑒: 𝐴𝑔 → 𝐴𝑔+ (𝑀1) + 𝑒 − Types of conductance: There are three type’s namely specific conductance, equivalence
0.0591
0
[𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠] 𝐴𝑡 𝐶𝑎𝑡ℎ𝑜𝑑𝑒: 𝐴𝑔+ (𝑀2) + 𝑒 − → 𝐴𝑔 Applications conductance, and molar conductance.
𝐸=𝐸 + 𝑙𝑜𝑔
𝑛 [𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠] 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.
0.0591 [𝐻𝑔2 𝐶𝑙2 ] 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
𝐸 = 𝐸0 + 𝑙𝑜𝑔 Equivalence conductance (λ) is the conductance of the solution when 1g equivalent weight of
𝑛 [𝐻𝑔]2 [𝐶𝑙]2− 4. In this method Oxidation-reduction titrations can also be carriedout.
0.0591 [𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠] 5. Precipitation reactions can also be carried outpotentiometrically. solution is placed between two electrodes of area 1cm2 at 1cm apart.
Since [Hg2Cl2] = [Hg] 2 = 1, the above equation becomes 𝐸 = 𝐸0 + 𝑙𝑜𝑔 Molar conductance (µ) is the conductance of the solution when 1g molecular weight of solute is
𝑛 [𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠]
0.0591 1 For example: placed between two electrodes of area 1cm2 at 1cm apart
0
𝐸=𝐸 + log − 𝐸 0 = 𝐸 0 𝐶𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸 0𝐴𝑛𝑜𝑑𝑒 Procedure: Pipette out 25cm3 of FAS solution into a 50 cm3 Application of Conductometric titration
2 [𝐶𝑙 ] It is used in the estimation of acids and bases present in the sample solutions. The possible
beaker. Add one test tube full of dil H2SO4. Immerse Pt. &
The calomel electrode potential is depending on the concentration of chloride ions in KCl. If the 0 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
Concentration of chloride ions increases, the potential decreases and vice versa. (The potential of a potentiometer. Fill the burette with K2Cr2O7 solution. Add Strong acid v/s strong base (HCl v/s NaOH)
calomel is inversely proportional to the concentration of chloride ions) 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
The potential of calomel electrode is measured with respect to SHE and it depends on 𝐸 =0+ 𝑙𝑜𝑔 𝑜𝑟 𝐸 = 𝑙𝑜𝑔 stir well and measure the potential after each addition. Continue decreases due to replacement
𝑛 [𝑀1] 𝑛 [𝑀1]
concentration of KCl solution used. 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
Conc. KCl 0.1N 1N Saturated KCl After the neutralization point, conductivity rapidly rises with further addition of NaOH because
Potentiometric Titration
Potential (V) 0.334V 0.281V 0.242V
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.
Applications:
C=1/R = Ω-1 or mho or siemen
1) Used to determine the potential of the otherelectrodes.
Theory: In this titration the amount of substance in the solution is determined by measuring the
2) It is commonly used as reference electrode in all potentiometricdeterminations. Theory:
emf between two electrodes that are dipped into the solution. When the metal M is immersed in
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.
Electrolytic Concentration Cell: 0.0591
It is galvanic cell, which consists of two identical electrodes, which are in contact with the same 𝐸 = 𝐸 0 + 𝑛 𝑙𝑜𝑔[𝑀𝑛+ ] According to ohm’s law the current flowing through the conductor is directly proportional to
solution of electrolyte in different concentrations. From this equation the potential of the electrode is directly proportional to the concentration of voltageand inversely proportional to the resistance.
Example: the ionic species present in the solution. I= or E=IR
Consider two silver electrodes that in contact with the AgNO3 solution of different The resistance of the any conductor is directly proportional to the length, inverselyproportional
concentrations (M1 and M2) connected through voltmeter. The electrolytes are connected through Instrumentation: to the area of cross section of the conductor Therefore R = S (l/a) where S is specific resistance
salt bridge. 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
The cell representation Ag/ AgNO3 (M1)// AgNO3 (M2)/Ag 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
Where M1 and M2 are the molar concentration of the Ag+ ions in the two half-cells. 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.

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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.

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Department of Chemistry, SVIT Page 13