ELECTROCHEMISTRY

INTRODUCTION
It is the study of the relation between 2 types of energy, electrical and chemical energies. When we put an electrolyte e.g. CuSO4 in a container and a Cu electrode is dropped in it, one of 2 phenomena happens 1- Ionic pressure: 2- Electrolytic solution pressure:

1- IONIC PRESSURE:

when the metal ion deposit on the metal rod.

Here, the rod become +vely charged and an equivalent ve charge will be created in the neighboring layer of the solution, and an electrical double layer is then formed.

2- ELECTROLYTIC SOLUTION PRESSURE:

When the rod itself is dissolute in its solution:

Where Zn-2 is now in the solution, the rod is vely charged and equivalent +ve charge will be created in the neighboring layer of the solution and an electrical double layer is then formed.

IMPORTANT NOTES

The thickness of the electrical double layer is very small about 0.01mm In fact both happen but one will be predominant than the other,once the electrical double layer is formed the 2 processes stop In both cases a potential difference between the electrode and bulk solution is formed, which is known as the electrode potential. The electrode which is the rod and its wire connection represents a half cell, when these wire connections are attached to another electrode they both together form a cell. According to IUPAC system electrode potential is ve if the charge is ve and vice versa, according to IS system if M+ electrode potential is ve and vice versa. e.g. Zn potential is 0.76 v, Cu potential is + 0.34 v both values are standard electrode potential

STANDARD ELECTRODE POTENTIAL :

It is the potential measured when the electrode is immersed in 1 Molar solution of one of its salts. Its value can be calculated from Nernst equation

E25C

= E + [RT/nF] Ln [M+n]

E25C = E + [0.059/N] LOG [M+N]

Where: E25C = Electrode potential at 25C E = Standard electrode potential R = Gas constant (8.314 k.cal.mol-1) T = absolute temperature by K scale = 273 + C n = Number of electrons transferred F = Faraday electricity quantity unit 96500 coulombs Ln = Natural logarithm = 2.303 log [M+] = Metal ion concentration (molar concentration)

NOTES

There are some very reactive metals e.g. Ni, Cr, Fe. In their solution the 2 processes mentioned before don't stop. This cause corrosion to its surface, so they cannot be used for the manufacture of electrodes. Some metals are inert metals which will not react with the solution. Such metals are called Nobel metals e.g. Au, Ag, Pt, Pd. These have special uses as redox reactions where electron transfer occur.

ACTIVITY COEFFICIENT:

This is for correction of Molar concentration of ions, e.g. we write [Mn+] only for simplicity, this formula is only correct if the metal is mono-valent and in very dilute solution. H2SO4, HCl are strong acids, but their degree of dissociation is 0.68 & 0.91 respectively sp HCl is more dissociated than H2SO4 thus more active.

ACTIVITY COEFFICIENT:

Activity coefficient depends on ionic strength and charge (valency). If ionic strength and charge , the activity coefficient e.g. For Fe3+/Fe2+, E for this system is 0.771 V E = E + [0.591/1] log [Fe3+]/[Fe2+] = E + [0.591/1] log 1= E By acidification of the solution with HClO4, E = 0.737 V which is much less than before and that is because we must multiply the equation with Activity coefficient where that of Fe3+ Fe2+ so the ratio in the previous equation will be a fraction not 1 thus

HOW TO CALCULATE IONIC STRENGTH () OF A SOLUTION:

= 1/2 [m1z12 + m2z22 + m3z32 + ] where: m = molar conc. of ion (+ve or ve) z = charge e.g. Calculate the of a solution containing 0.01 M NaNO3 and 0.02 M Mg(NO3)2 answer:

QUESTION :

Calculate solubility product ksp of ZnS if the potential of Zn electrode is dipped into a saturated solution of ZnS, E = -10 v, E = - 0.76 v

N.B. ksp is the product of molar concentration and it is only calculated for substances insoluble in water. Ksp = [Zn2+][S2-] = [Zn2+]2, when saturated solution of ZnS, the dissolved part = ksp E = E + [0.591/2] log [Zn2+] -1 = - 0.76 + 0.06/2 log [Zn2+] [Zn2+] = 10-8M & ksp = 10-16

TYPES OF ELECTRODES
A:

According to activity B: According to charge C: according to the potential

A: ACCORDING TO ACTIVITY

1- Active:

2- Inert (Nobel metal) e.g. Au, Ag, Pt, Hg

B: ACCORDING TO CHARGE

1- Cathode: at which reduction process occur i.e. gain of electron

2- Inert (Nobel metal) e.g. Au, Ag, Pt, Hg

C: ACCORDING TO THE POTENTIAL

1- Reference electrode: having known and constant potential 2- Indicator electrode: having potential dependent on the conc. according to Nernst equation 3- Auxillary electrode: Nobel Metal, where it does not lose or gain electrons, only electron transfer occur (used in voltamtry).

LAWS OF ELECTROCHEMISTRY

1- Ohm's law: E = iR
E = Potential (Volt) v, measured by voltammeter i = Current (Ampere) A, measured by Galvanometer not ammeter R = Resistance (Ohm)

2- Faraday's law: Q = it
Q = Quantity of electricity(coulomb) measured by coulometer i = intensity of current (A) t = Time in seconds

ELECTROCHEMICAL METHODS

1- Potentiometry: potential is measured of indicator electrode against reference electrode under zero current conditions i.e. when there is no transfer of electrons 2- Conductometry: measures the ability of a substance to conduct electricity, where conductance = 1/R. the 2 electrodes used are identical and usually inert e.g. Pt 3- Voltammetry: Polarography is a class of it. The intensity of current is measured where it is proportional to the conc. i C

ELECTROCHEMICAL CELL

1- Galvanic cell: Produces electricity

It is composed of 2 half cells connected together through a salt bridge that must be present to conduct electricity. N.B. Salt bridge: is agar saturated with salt that should be strong electrolyte and whose 2 ions have the same ionic mobility e.g. KCl

ELECTROCHEMICAL CELL

Electrolysis cell: consumes electricity

Composed of 2 identical electrodes of Nobel metal and a source of electricity (battery) It is used in electroplating e.g. with AuCl3 when current is passed the Au is precipitated on the electrode while Cl2 gas is evolved.

PROBLEMS

1- Calculate the potential of Ag electrode in a solution saturated with AgI and has I- activity C = conc. of exactly 1 ksp of AgI = 8.310-17, E = -0.799 V. 2- what is the potential for half cell of system of Cd electrode immersed in solution which is 0.015 M of [Cd++], E = 0.405 V. 3- Calculate the potential for Pt electrode immersed in a solution prepared by saturating 0.015 M solution of KBr with Br2. E = 1.055 V 4- calculate the potential for Pt electrode immersed in solution of 0.015 KBr and 110-3 Br2

TYPES OF ELECTRODES
There

are two types of electrodes, reference electrodes and indicator electrodes. The first type of which the reference electrodes are of constant known potential.

A: REFERENCE ELECTRODES:
Types of reference electrodes: 1- Normal Hydrogen electrode (NHE) or (SHE): 2- Saturated Calomel electrode (SCE): 3- Ag/AgCl electrode:

1- NORMAL HYDROGEN ELECTRODE (NHE) OR (SHE):

Other names: standard or saturated hydrogen electrode.

Other names: standard or saturated hydrogen electrode. It is composed of a glass tube with a sheet of platinum in the middle. The platinum sheet is covered with Pt black "finely divided platinum". A stream of H2 gas is pumped under atmospheric pressure so that H2 is adsorbed on the surface of the platinum

1- NORMAL HYDROGEN ELECTRODE (NHE) OR (SHE):

According to Nernst equation: E = E (0.059/2) log [H+]2/[H2] Conc. of gas = its pressure, so [H2] = 1 E = E 0.059 log [H+] E = 0 - 0.059 log [H+] E = 0.059 pH N.B. The electrode is also called potentiometer, and has 2 scales pH 0 14 Potential 0 1000 volts Disadvantages of (NHE): By time the H2 is desorbed from the platinum sheet It is hard to be handled (inconvenience) Its t1/2 is about 7-20days not used frequently

2- SATURATED CALOMEL ELECTRODE (SCE):

It is composed of a paste of Hg2Cl2, Hg0 and KCl wrapped in a gauze and suspended inside glass tube having a plug with small opening. An 0.1 molar, 1 molar or saturated solution of KCl is placed inside the glass electrode. The diffused KCl through the terminal plug acts as a salt bridge completing the circuit when the electrode is placed in the solution being detected. As the solution inside the electrode decreases by time, a fresh solution can be injected through the upper opening by a

2- SATURATED CALOMEL ELECTRODE (SCE):

The best conc. of KCl to be used is the saturated solution where crystals of KCl are present. In hot atmosphere solution may expand which will lead the concentration to change in both the 0.1 molar and the 1 molar solution while crystals in the saturated solution will dissolve keeping the net conc. constant. E for : 0.1 molar KCl = 0.32 V 1 molar KCl = 0.28 V Saturated solution of KCl (4.2 molar) = 0.24 V Disadvantage of (SCE) Not used above 80C temperature Can't be used in solutions with high Cl- conc. as the KCl diffusion through the terminal plug will be hindered To use such electrode with these solution, the Hg2Cl2 can be replaced with Hg2SO4 and KCl with K2SO4.

2- SATURATED CALOMEL ELECTRODE (SCE):

E = E + (0.059/2) log [Hg2Cl2]/[Hg0][Cl-]2 E = E + 0.059/2 log 1/[Cl-]2 E = E (0.059/2) log [Cl-]2 E = E 0.059 log [Cl-] E = E + 0.059 pCl

3- AG/AGCL ELECTRODE:

N.B. there is a difference between Ag/AgCl electrode and Ag electrode, where the first is a reference electrode while the second is an indicator electrode.
It is composed of a glass tube containing an Ag wire coated with AgCl which is the main substance in the electrode reaction. AgCl is highly insoluble in water with resistance 2000-3000 , if it could transfer electric current this would lead to change in its potential thus it wouldn't have been used as reference electrode. The glass tube also contain a saturated solution of KCl, and in its bottom there is asbestos fibers that would allow the diffusion of KCl that also acts here as the salt bridge.

3- AG/AGCL ELECTRODE:

N.B. there is a difference between Ag/AgCl electrode and Ag electrode, where the first is a reference electrode while the second is an indicator electrode E = E + 0.059 log [AgCl]/[Ag0][Cl-] E = E + 0.059 log 1/[Cl-] E = E - 0.059 log [Cl-] E = E + 0.059 pClE is a constant value = 0.222 V Advantages of Ag/AgCl electrode: It can be used until temperature about 270C It can be used in non aqueous media .

B: INDICATOR ELECTRODES:

In these types of electrodes, the potential changes with the conc. of analytes according to Nernst equation. Indicator electrodes are of types:
Metal electrode Electrodes of first kind Electrodes of second kind Inert electrodes Membrane electrode Crystalline Non-crystalline

METAL ELECTRODE
1)

2)
3)

Metal electrodes of first kind Metal electrodes of second kind Inert electrode:

METAL ELECTRODES OF FIRST KIND:

It is used to determine cations of the same material i.e. to determine Cu2+ cupper electrode is used and to determine Zn2+ Zinc electrode is used. It is only used for metals where an equilibrium exists between the metal and its ion, e.g. Metals like Ni, Fe, Co are very reactive thus can't be used to manufacture electrode as by time they undergo corrosion Examples for metals that can be used to make such type of electrodes are: Cu, Zn, Cd, Pt, Ag

METAL ELECTRODES OF FIRST KIND:

E = E + [0.059/2] log [Cu2+] E = E - 0.03 pCu2+ Graphical representation of the relation between E and pCu2+

METAL ELECTRODES OF SECOND KIND:

It is used to determine anions, it is composed of a metal that forms with the determined anion insoluble salt, or complex ion. e.g. to determine I-, Cl-, Br- and SCN- , Ag electrode is used. N.B. a complex ion is soluble in water but it is non-ionized e.g. Ag(CN)2 silver argento cyanide where its energy content is very low.

FOR THE DETERMINATION OF KCL

An Ag electrode is used as an indicator electrode. The solution is saturated with one crystal of AgCl.

Problem: Calculate the conc. of KI sample if Ag electrode immersed in a solution has potential of 0.472 v. E = -

FOR THE DETERMINATION OF KCL

E = E + 0.059 log [AgCl]/[Ag0][ Cl -] E = E + 0.059 log 1/[Cl-] E = E - 0.059 log [Cl -] E = E + 0.059 p Cl Graphical representation of the relation between E and p Cl -

FOR THE DETERMINATION OF EDTA

In such case a mercury electrode is used, and the solution is saturated with mercury-EDTA(HgY-2) of known concentration.

INERT ELECTRODE:

It is composed of one of the Nobel metals, e.g. Au, Pt, Hg, and C which is considered also to be a Nobel metal as at very high pressure it forms diamond. Such electrode is used in the determination of electro-active substances where there is electron transfer. As it is not affected by redox systems nor acid-base systems. Thus the potential difference does not depend on the material of the electrode. e.g. for systems determined by Nobel electrodes: Fe3+/Fe2+ where E in this case = 0.77 Ce4+/Ce3+ E = 1.43 And E = E + 0.059/n log [Fe3+]/[Fe2+]

NON-METAL ELECTRODES

GLASS ELECTRODE:

It is composed of a Hard glass tube of about 10-15 cm long which is composed of SiO2. The terminal of the tube is composed of a bulb of 1.5-2 cm which is made of a pH sensitive glass that is composed of SiO2 with other oxides. e.g.: 20% Na2O + 10% CaO + 70% SiO2 27% AlO3 + 5% CaO + 68% SiO2 This kind of electrode is mainly used to determine [H+], i.e. used to determine the pH of solutions. In its interior there is internal reference electrode which is usually Ag/AgCl electrode in a solution of KCl of known concentration and buffer solution of high capacity to adjust the pH

GLASS ELECTRODE:
The bulb of the electrode should be always soaked in water otherwise it will crack, upon soaking in water the hydration occurs in a rate of 50mg H2O/cm3 Water reacts with the SiO2 forming a gel layer of silicic acid (H2SiO3) of about 10-4-10-5 mm thickness. Through this gel layer ion exchange occur between the Hydrogen ions in the solution being detected + H (in solution) + Na+ (in Glass) and the sodium ions in the solution) glass.

H+ (in Glass) + Na+ (in

GLASS ELECTRODE:

Ecell = Eg - Eref Ecell = Eg 0.059 pH 0.059 PH = Eg - Ecell pH = (Eg - Ecell)/0.059

GLASS ELECTRODE:

To calculate the Eg we must put in consideration that: The difference in concentration between hydrogen ions in the detected solution and those accumulated on the outer surface of the glass cause potential difference V1 V1 = J1 + 0.059 log [H1+]/[H\1+] The difference in concentration between hydrogen ions accumulated on the inner surface of the glass and in those in the solution inside the electrode also causes a potential difference V2 V2 = J2 + 0.059 log [H2+]/[H\2+] Eg = V 1 - V2

GLASS ELECTRODE:

Eg = V1 - V2
Eg = J1 + 0.059 log [H1+]/[H\1+] - J2 - 0.059 log [H2+]/[H\2+]

When the glass is of high quality, J1 will be = to J2 [H\1+] will be = [H\2+] Therefore, Eg = 0.059 log ([H1+]/[H\1+] [H\2+]/[H2+]) Thus Eg = 0.059 log [H1+]/[ H2+] Eg = 0.059 log [H1+] 0.059 log [ H2+] N.B. [H2+] is the concentration of hydrogen ions in the buffer solution within the electrode, which is known

GLASS ELECTRODE:
Advantages: 1) Responsive to cations irrespective to the accompanying anion. i.e. will detect the H+ present in the solution regardless the type of anion present. 2) Can be used in organic solvents, but should be firstly soaked in water 3) Can be used for fat soluble substances 4) Not affected by redox systems 5) Not affected by common electrode poisoning e.g. S2- and proteins. 6) Its response is rapid (within few seconds).

GLASS ELECTRODE:
Disadvantages: 1) pH ranges 2-12, where less than 2 there will be an error where the reading will be less than the correct reading, and above 12 the reading will be higher than the correct one, and this is because when there is a very high concentrations of either H+ or OH-, the activity of the ions change. 2) Can not be used at high concentration of Fwhere, 3) F- + H+ HF 4) HF + H2SiO3 H2SiF6 + H2O

QUINHYDRONE ELECTRODE:

It is a tube containing equimolar mixture of quinine and hydroquinone

O OH

2e

2H+

Pt

OH

QUINHYDRONE ELECTRODE:
E = E + 0.059/2 log ([Q][H+]2)/[HQ] Since [Q] = [HQ] = 1 Therefore, E = E + 0.059 log [H+] E = E - 0.059 pH E is a constant value here = 0.7 V Thus E = 0.7 0.059 pH Thus potential depends on the pH, therefore it is used to determine hydrogen ion concentration.

QUINHYDRONE ELECTRODE:

Graphical representation:

QUINHYDRONE ELECTRODE:

To determine the pH of a solution sample:

Ecell = EQhyd SCE Ecell = 0.7 0.059 PH 0.246 Ecell = 0.454 0.059 pH 0.059 pH = 0.454 - Ecell pH = (0.454 - Ecell)/0.059

QUINHYDRONE ELECTRODE:
Disadvantages: 1) PH range (5-9) At PH > 9 there will be high concentration of OHwhich will dissolve the hydroquinone due to the acidic properties its phenolic OH possess. And thus the concentration of quinine to hydroquinone will be no longer equimolar.
OH O-

2 OH-

2H 2O

OH

O-

Phenate

2)

It can not be used with oxidizing/reducing agents, as the main reaction of the electrode is a redox reaction. Thus the presence of any oxidizing/reducing agent

ANTIMONY ELECTRODE:

It is composed of a wire of antimony which is covered with antimony oxide.

Sb2O3

6e

6H+

2Sb

3H2O

E = E + 0.059/6 log ([Sb2O3][H+]6)/[Sb] [Sb2O3] = [Sb] = 1 Therefore, E = E + 0.059 log [H+] E = E - 0.059 pH

ANTIMONY ELECTRODE:

Graphical representation:

Disadvantages: 1) Affected by redox systems 2) Highly affected by electrode poisoning systems e.g. proteins 3) Limited PH range

SINGLE CRYSTAL ELECTRODE:

In this kind of electrode, ion exchange occurs on the surface of the crystal e.g. Fluoride electrode is Fluoride electrode.

composed of a glass tube containing an internal reference electrode which is usually Ag/AgCl electrode in a solution containing 1 M KCl and 1 M KF. In the bottom of this glass tube a crystal of lanthanum fluoride is present. The crystal should be

SINGLE CRYSTAL ELECTRODE:

E = E + 0.059 log ([F-] in internal solution/[F-] in external solution) [F-] in internal solution = 1 Thus, E = E + 0.059 log 1/[F-] E = E - 0.059 log [F-] E = E + 0.059 PF

SINGLE CRYSTAL ELECTRODE:

Advantages

of Fluoride

electrode:

It can determine the [F-] in the presence of 1000 times of Cl-, Br-, I-, NO3-, HCO3-, SO4--.

Uses:

It is used to determine fluoride ion concentration in : 1) Drinking water 2) Pharmaceutical preparations 3) Bone, blood and biological fluids

MIXED CRYSTAL ELECTRODE:

It is composed of the highly insoluble Ag2S along with other crystal according to the detected species. For the determination of cations: To determine Cu++ Ag2S + CuS To determine Cd++ Ag2S + CdS To determine Zn++ Ag2S + ZnS For the detection of anions: To determine Cl- Ag2S + AgCl To determine Br- Ag2S + AgBr To determine I- Ag2S + AgI These kinds of electrodes give direct measuring

MOLECULAR SELECTIVE ELECTRODE

Used for determination of intact molecules

1- GAS SELECTIVE ELECTRODE:

It used for detection of gases dissolved in water e.g. CO2 ions that form gases upon pH control.
NO2nitrite ion H+ NO2 gas NO gas H2O

Gas selective electrode is composed of electrochemical cell with ion selective electrode with a membrane that allows the passage of gases from the test solution to the electrode. To determine the CO2 in a test solution, the thin membrane allow its passage by effusion to be entrapped in the layer sandwiched between glass electrode and the membrane. CO2 afterwards dissolve in the water found in this layer + ion that can be then detected by - the glass + forming H HCO H CO H O 3 2 2 electrode.

1- GAS SELECTIVE ELECTRODE:

1) 2) 3)

Membranes are of 2 types 1- Homogenous membrane:

It is the thinner type of membrane pore size (0.01-0.03 mm) It is hydrophobic in nature and usually made of silicon rubber. Gas dissolve in the membrane until it is saturated with the gas- then it diffuses, dissolves and moves into the internal solution of the membrane

1) 2) 3) 4) 5)

2- Micro-porous membrane:
It is a hydrophobic polymer composed of poly tetrafluoro ethylene and poly propylene. It repels water and electrolytes and only passes gases only Porosity = 70% void volume Pore size = 1m Thickness = 0.1 m

1- GAS SELECTIVE ELECTRODE:

1- GAS SELECTIVE ELECTRODE:

1- GAS SELECTIVE ELECTRODE:

2- ENZYME ELECTRODE:

Enzyme electrode is another type of molecular selective electrodes, where the enzyme is immobilized on an electrode by which it inters the reaction and the product is finally obtained. The enzyme electrodes are also termed enzyme probe electrodes, as the enzyme inters the chemical reaction producing a product that is being afterwards detected by another type of detector.

Advantages of enzyme electrode:

After the immobilization of the enzyme on the electrode, it could be used for 100 times and this overcomes the problem of its being expensive They are specific They can be used for biological samples in which chemical methods are hard to use They are free from interferences

Disadvantages of enzyme electrode:

It is very expensive

2- ENZYME ELECTRODE:
Methods of enzyme immobilization on electrode surface:
1) 2)

3) 4)

Physical entrapment in polymer gel Physical adsorption on solid material e.g. Al2O3 or glass beads Covalent bonding with a polymer Co-polymerization using different monomers

2- ENZYME ELECTRODE:

Electrode for measuring Blood Urea Nitrogen

The following example is for enzyme separate electrode, where the enzyme is in a separate cartilage and the sensor is in another compartment.

2- ENZYME ELECTRODE:
How the enzyme detector works for the determination of Blood Urea Nitrogen:
1) 2)

3) A. B.

The sample is injected in the pump (about 20 l) Buffer solution (PH = 7.5) is passed so that the reaction takes place and urea is hydrolyzed according to the previous eq. giving HCO3-, NH4+ Activation step follows, by either: Passing a base so that to produce NH3 gas that can be detected by ammonia electrode Passing an acid so that to produce CO2 gas that can be detected by glass electrode.

2- ENZYME ELECTRODE:

2- ENZYME ELECTRODE:

Other enzyme electrodes:

Limitation of this type of enzyme electrode where the enzyme is in same compartment with the sensoris that it is used in limited PH environment, as each enzyme has an optimum at which it only reacts.

LIQUID/LIQUID ELECTRODE
Liquid/liquid electrode is used to directly determine polyvalent cations:

LIQUID/LIQUID ELECTRODE

When used to determine Ca2+ a standard solution of CaCl2 is used, where a standard solution is a solution of known concentration e.g. 1 M. Ion exchange: is of a high molecular weight , containing acidic, basic or chelating groups. e.g. Diphosphate ester ion exchange ((RO)POO)2 where R = C16-C18 |The pores of the membrane should be saturated with the ionexchange substance by wick action. Before the sample is introduced, the ion exchange should be exposed to a solution of the same substance

LIQUID/LIQUID ELECTRODE

In this case:
There will potential difference on the surface of the membrane. This will be measured by the external reference electrode. There will also be a potential difference inside the electrode, that will be measured by the internal reference electrode.

Therefore,
E = k + 0.059/2 log [Ca2+]

a known concentration of Ca2+. [Ca2+] here represents the activity rather than the concentration as it is a divalent cation. N.B Only in monovalent cations and diluted solutions the activity = concentrations.

Where: E = the difference between the 2 potentials K: the reaction rate constant can be determined when using

APPLICATIONS

1- DIRECT POTENTIOMETRY
Where the reference electrode and the indicator electrode are placed in the sample solution, giving a direct reading of the tested substance. e.g.1 pH in pH meter e.g.2 Fluoride electrode for fluoride ion e.g.3 liquid/liquid electrode for Ca2+ directly in milk or in biological fluids.

2- POTENTIOMETRIC TITRATION:

It is the usage of Potentiometric methods in the determination of the concentration of pharmaceutical preparations accompanying titration techniques. e.g. in the non-aqueous titration of basic compounds which may contain 1ry, 2ry, or 3ry amines, or hydrazine containing compounds. Those are considered weak bases, thus the conventional titrational methods cannot be applied, instead the non-aqueous titration is used, where the sample is dissolved in highly acidic solvent e.g. glacial acetic acid, then it is titrated against perchloric acid. The Potentiometric method can be used here where the excess perchloric acid after the consumption of the titrated base will change the PH of the solution that can be detected by the PH meter indicating end

2- POTENTIOMETRIC TITRATION:

ZERO ORDER CURVE

By plotting a curve between the change in pH and ml of Perchloric acid added, the EP can be determined where it will be the point at which inflection of PH occurs

FIRST ORDER DERIVATIVE CURVE

This S shaped curve is much more precise when the reaction occurs between a stronger base and a stronger acid, but when most detected sample are weaker. The curve usually obtained is sluggish, this is solved by plotting a first derivative curve, where the curve is plotted for the change of PH over the change of ml Titrant, Against ml of Titrant.

SECOND ORDER DERIVATIVE CURVE

If a very week base is being titrated the last plot may not even be efficient, thus a first derivative of the first derivative (second derivative) is being plotted. This is indeed is the most accurate. 2PH/V2 against volume of titrant

TITRATION CURVES

In all case titration should be completed furthermore after reaching the end point to get the most accurate EP from the curve, thus the most accurate as end point cannot be missed. N.B. to plot this curve certain values should be calculated first

E/V 2E/V2

Where V= volume of Titrant added E is the potential produced equivalent to PH V is the difference in volume of Titrant added E is the change in potential produced equivalent to the change of PH due to the addition of Titrant. 2E/V2 is calculated through the following equation: 2E/V2 = [(E/V)2 (E/V)1]/ V

ADVANTAGES OF POTENTIOMETRIC TITRATION:

1) 2)

Can be applied to colored or turbid solutions where end point can't be detected visually Can be applied to weak bases or weak acids, where the end point detection is also hard visually. N.B. USP validates the Potentiometric titration methods rather than visual indicator methods For N containing compounds, they are usually basic compounds e.g. amines, except if the atom next to N is electron withdrawing. In this case the compound is rather acidic. Non-aqueous titration is also applied for raw materials before being incorporated in pharmaceutical formulations. Weak basic compounds are dissolved in glacial acetic