Engg Chemistry

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CMRIT Redefining Quality

Lecture notes:

UNIT 1 ELECTROCHEMISTRY AND BATTERIES:

1.1 .Concept of Electro Chemistry:

The study of the processes involved in the inter conversion of

electrical energy and chemical energy is known as electro chemistry.

Conductance-electrolyte in solution:

Ohms law states that the resistance of a conductor is directly

proportional to its length and inversely proportional to its area of cross

section.

R = .l/A

Where R = resistance (ohm)

= specific resistance or resistivity

l = length (cm)

A = area of cross section (cm2)Specific conductance, Equivalent conductance and molar conductance:

Specific conductivity (k) :

The reciprocal of specific resistance or resistivity of an electrolytic

solution is known as specific conductivity.

Unit : ohm-1

cm-1

or S cm-1

Equivalent Conductivity (eq) :

The conductance of all the ions present in 1 equivalent of the

electrolyte present in the given solution at a given dilution is known as

equivalent conductivity.

Unit : ohm-1

cm2

eq-1

Molar Conductivity (m):

The conductance of all the ions present in one mole of the electrolyte

present in the given solution at a given dilution is known as molar

conductivity.

Unit : ohm-1

cm2

mol-1

Variation of specific conductivity with dilution:

Specific conductivity depends on the following factors:

(1)the number of ions(2)the amount of water present.

As the dilution i.e., the amount of water increases, the conducting power of

1 cm3of the electrolytic solution decreases.

I B.Tech Engineering Chemistry1

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Variation of Equivalent Conductivity with dilution:

The conducting power of an electrolyte is due to the ions present and

this increases with increase in the dilution. The equivalent or molar

conductivity increases as the number of ions present in a solution having one

equivalent or one mole of electrolyte increases with dilution.

1.2 KOHLRAUSCH'S LAW

"At infinite dilution, when dissociation is complete, each ion makes a

definite contribution towards equivalent conductance of the electrolyte

irrespective of the nature of the ion with which it Is associated and the value

of equivalent conductance at infinite dilution for any electrolyte is the sum

of contribution of its constituent ions", i.e., anions and cations. Thus,

/\ = a + c

The and are called the ionic conductance of cation and anion at infinite

dilution respectively. The ionic conductances are proportional to their ionic

mobilities. Thus, at infinite dilution,

c = kuc and a = kua

where uc and ua are ionic mobilities of cation and anion respectively at

infinite dilution. The value of k is equal to 96500 c, i.e., one Faraday.

Thus, assuming that increase in equivalent conductance with dilution is dueto increase in the degree of dissociation of the electrolyte; it is evident that

the electrolyte achieves the degree of dissociation as unity when it is

completely ionized at infinite dilution. Therefore, at any other dilution, the

equivalent conductance is proportional to the degree of dissociation. Thus,

Degree of dissociation, = /\/(/\ )

=(Equivalent conductance at a given concentration)/(Equivalent

conductance at infinite dilution)

1.3 Galvanic cells:

A Galvanic cell consists of two half-cells. In its simplest form, each half-cell

consists of a metal and a solution of a salt of the metal. The salt solution

contains a cation of the metal and an anion to balance the charge on the

cation. In essence the half-cell contains the metal in two oxidation states and


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the chemical reaction in the half-cell is an oxidation-reduction (redox)

reaction, written symbolically in reduction direction as

Mn+

(oxidized species) + n e M (reduced species)

In a galvanic cell one metal is able to reduce the cation of the other and,conversely, the other cation can oxidize the first metal. The two half-cells

must be physically separated so that the solutions do not mix together. A salt

bridge or porous plate is used to separate the two solutions.

The number of electron transferred in both directions must be the same, so

the two half-cells are combined to give the whole-cell electrochemical

reaction. For two metals A and B:

An+

+ n e A

Bm+

+ m e Bm A + n Bm+ n B + m An+

This is not the whole story as anions must also be transferred from one half-

cell to the other. When a metal in one half-cell is oxidized, anions must be

transferred into that half-cell to balance the electrical charge of the cation

produced. The anions are released from the other half-cell where a cation is

reduced to the metallic state. Thus, the salt bridge or porous membrane

serves both to keep the solutions apart and to allow the flow of anions in the

direction opposite to the flow of electrons in the wire connecting the

electrodes.

The voltage of the Galvanic cell is the sum of the voltages of the two half-

cells. It is measured by connecting a voltmeter to the two electrodes. The

voltmeter has very high resistance, so the current flow is effectively

negligible. When a device such as an electric motor is attached to the

electrodes, a current flows and redox reactions occur in both half-cells. This

will continue until the concentration of the cations that are being reduced

goes to zero.

For the Daniel cell, depicted in the figure, the two metals are zinc and

copper and the two salts are sulfates of the respective metal. Zinc is the more

reducing metal so when a device is connected to the electrodes, the

electrochemical reaction is

Zn + Cu2+Zn2+ + Cu


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The zinc electrode is dissolved and copper is deposited on the copper

electrode. By definition, the cathode is the electrode where reduction (gain

of electrons) takes place, so the copper electrode is the cathode. The cathode

attracts cations, so has a negative charge. In this case copper is the cathode

and zinc the anode.

Galvanic cells are typically used as a source of electrical power. By their

nature they produce direct current. For example, a lead-acid battery contains

a number of galvanic cells. The two electrodes are effectively lead and lead

oxide.

1.4 Reference electrode:

Saturated calomel electrode

The Saturated calomel electrode (SCE) is a reference electrode based on thereaction between elemental mercury and mercury (I) chloride. The aqueous

phase in contact with the mercury and the mercury (I) chloride (Hg2Cl2,

"calomel") is a saturated solution ofpotassium chloride in water. The

electrode is normally linked via a porous frit to the solution in which the

other electrode is immersed. This porous frit is a salt bridge.

In cell notation the electrode is written as:

Theory of operation

The electrode is based on the redox reaction

The Nernst equation for this reaction is

where E0

is the standard electrode potential for the reaction and a Hg is the

activity for the mercury cation (the activity for a liquid is 1). This activity

can be found from the solubility product of the reaction


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By replacing the activity in the Nernst equation with the value in the

solubility equation, we get

The only variable in this equation is the activity (or concentration) of the

chloride anion. But since the inner solution is saturated with potassium

chloride, this activity is fixed by the solubility of potassium chloride. When

saturated the redox potential of the calomel electrode is +0.2444 V vs. SHE

at 25 C, but slightly higher when the chloride solution is less than saturated.

For example, a 3.5M KCl electrolyte solution increases the reference

potential to +0.250 V vs. SHE at 25 C, and a 0.1 M solution to +0.3356 V

at the same temperature.

Application

The SCE is used in pH measurement, cyclic voltammetry and general

aqueous electrochemistry.

This electrode and the silver/silver chloride reference electrode work in the

same way. In both electrodes, the activity of the metal ion is fixed by the

solubility of the metal salt.

The calomel electrode contains mercury, which poses much greater health

hazards than the silver metal used in the Ag/AgCl electrode.

Quinhydrone electrode:

The quinhydrone electrode is a type ofredoxelectrode which can be used to

measure the hydrogen ion concentration (pH) of a solution in a chemical

experiment. It provides an alternative to the commonly used glass electrode

in a pH meter.

The electrode consists of an inert metal electrode (usually aplatinum wire)

in contact with quinhydrone crystals and a water-based solution.

Quinhydrone is slightly soluble in water, dissolving to form a mixture of two

substances, quinone and hydroquinone, with the two substances present at


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equal concentration. Each one of the two substances can easily be oxidised

or reduced to the other.

The potential at the inert electrode depends on the ratio of the activity of two

substances (quinone-hydroquinone), and also the hydrogen ion

concentration. The electrode half-reaction is:

Hydroquinone Quinone + 2H+

+2e-

Because the electrode half-reaction involves hydrogen ions, the electrode

potential depends on the activity of hydrogen ions. From the Nernst

equation:

For practical pH measurement, a second pH independent reference electrode

(such as a silver chloride electrode) is also used. This reference electrode

does not respond to the pH. The difference between the potential of the two

electrodes depends (primarily) on the activity of H+ in the solution. It is this

potential difference which is measured and converted to apH value.

The quinhydrone electrode is not reliable above pH 8. It is also unreliable in

the presence of strong oxidising or reducing agents, which would disturb the

equilibrium between hydroquinone and quinone. It is also subject to errors in

solutions containing proteins or high concentrations of salts

Other electrodes commonly used for measuring pH are the antimony-

antimony oxide electrode, the glass electrode and the hydrogen electrode.

1.5 Ion selective electrode:

An ion-selective electrode (ISE), also known as a specific ion electrode

(SIE), is a transducer (orsensor) that converts the activity of a specific ion

dissolved in a solution into an electricalpotential, which can be measured by

a voltmeter orpH meter. The voltage is theoretically dependent on thelogarithm of the ionic activity, according to the Nernst equation. The sensing

part of the electrode is usually made as an ion-specific membrane, along

with a reference electrode. Ion-selective electrodes are used in biochemical

and biophysical research, where measurements of ionicconcentration in an

aqueous solution are required, usually on a real time basis.


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Types of ion-selective membrane:

There are four main types of ion-selective membrane used in ion-selective

electrodes: glass, solid state, liquid compound electrode.

Glass membranes:

Glass membranes are made from an ion-exchange type of glass (silicate or

chalcogenide). This type of ISE has good selectivity, but only for several

single-charged cations; mainly H+, Na

+,and Ag

+. Chalcogenide glass also

has selectivity for double-charged metal ions, such as Pb2+

, and Cd2+

. The

glass membrane has excellent chemical durability and can work in very

aggressive media. A very common example of this type of electrode is the

pH glass electrode.

Nernst equation:

In electrochemistry, the Nernst equation is an equation that can be used to

determine the equilibrium reduction potential of a half-cell in an

electrochemical cell. It can also be used to determine the total voltage

(electromotive force) for a full electrochemical cell. It is named after the

German physical chemist who first formulated it, Walther Nernst.

Expression:

The two (ultimately equivalent) equations for these two cases (half-cell, fullcell) are as follows:

(half-cell reduction potential)

(total cell potential)

where

Ered is the half-cell reduction potential at the temperature of interest

Eored is the standard half-cell reduction potential

Ecell is the cell potential (electromotive force)

Eocell is the standard cell potential at the temperature of interest

R is the universal gas constant:

T is the absolute temperature


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a is the chemical activity for the relevant species, where aRed is the

reductant and aOx is the oxidant. aX = XcX, where X is the activity

coefficient of species X. (Since activity coefficients tend to unity at

low concentrations, activities in the Nernst equation are frequently

replaced by simple concentrations.)

F is the Faraday constant, the number of coulombs per mole ofelectrons:

z is the number of moles ofelectrons transferred in the cell reaction or

half-reaction

Q is the reaction quotient.

At room temperature (25 C), RT/F may be treated like a constant and

replaced by 25.693 mV for cells.

The Nernst equation is frequently expressed in terms of base 10 logarithms

(i.e., common logarithms) rather than natural logarithms, in which case it iswritten, for a cell at 25 C:

The Nernst equation is used in physiology for finding the electric potential

of a cell membrane with respect to one type ofion.

1.7 Concentration cell

A Concentration cell is an electrochemical cell that has two equivalent half-

cells of the same material differing only in concentrations. One can calculate

the potential developed by such a cell using the Nernst Equation. A

concentration cell produces a voltage as it attempts to reach equilibrium,

which will occur when the concentration in both cells are equal.

Concentration cell methods of chemical analysis compare a solution of

known concentration with an unknown, determining the concentration of the

unknown via the Nernst Equation or comparison tables against a group ofstandards. Concentration cell corrosion occurs when two or more areas of a

metal surface are in contact with different concentrations of the same

solution. There are three general types of concentration cells:

Metal ion concentration cells


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In the presence ofwater, a high concentration of metal ions will exist under

faying surfaces and a low concentration of metal ions will exist adjacent to

the crevice created by the faying surfaces. An electrical potential will exist

between the two points. The area of the metal in contact with the high

concentration of metal ions will be cathodic and will be protected, and the

area of metal in contact with the low metal ion concentration will be anodicand corroded.

Oxygen concentration cells

Water in contact with the metal surface will normally contain dissolved

oxygen. An oxygen cell can develop at any point where the oxygen in the air

is not allowed to diffuse uniformly into the solution, thereby creating a

difference in oxygen concentration between two points. Corrosion will occur

at the area of low-oxygen concentration which are anodic.

Active-passive cells

For metals that depend on a tightly adhering passive film (usually an oxide)

for corrosion protection, salt that deposits on the metal surface in the

presence of water, in areas where the passive film is broken, the active metal

beneath the film will be exposed to corrosive attack. An electrical potential

will develop between the large area of the cathode (passive film) and the

small area of the anode (active metal). Rapid pitting of the active metal will

result.

Galvanic cells

Non-

rechargeable:

primary cells

Alkaline battery Aluminium battery

Bunsen cell Chromic acid cell Clark

cell Daniell cell Dry cell Grove cell

Leclanch cell Lithium battery

Mercury battery Nickel oxyhydroxide

battery Silver-oxide battery Westoncell Zamboni pile Zinc-air battery

Zinc-carbon battery

Rechargeable:

secondary

Lead-acid battery Lithium air battery

Lithium-ion battery Lithium-ion


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10/201


cells polymer battery Lithium iron phosphate

battery Lithium sulfur battery Lithium-

titanate battery Nickel-cadmium

battery Nickel hydrogen battery

Nickel-iron battery Nickel-metal

hydride battery Low self-dischargeNiMH battery Nickel-zinc battery

Rechargeable alkaline battery Sodium-

sulfur battery Vanadium redox battery

Zinc-bromine battery

Kinds of cells

Battery Concentration cell Flow

battery Fuel cell Trough battery

Voltaic pile

Parts of cells

Anode Catalyst Cathode Electrolyte

Half cell Ions Salt bridge

Semipermeable membrane

1.8 Galvanic series:

The galvanic series (or electro potential series) determines the nobility of

metals and semi-metals. When two metals are submerged in an electrolyte,

while electrically connected, the less noble (base) will experience galvanic

corrosion. The rate of corrosion is determined by the electrolyte and thedifference in nobility. The difference can be measured as a difference in

voltage potential. Galvanic reaction is the principle upon whichbatteries are

based.

Galvanic series (most noble at top)

The following is the galvanic series for stagnant (that is, low oxygen

content) seawater. The order may change in different environments.

Graphite

Palladium

Platinum

Gold

Silver

Titanium


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Stainless steel 316 (passive)

Stainless Steel 304 (passive)

Siliconbronze

Stainless Steel 316 (active)

Monel 400

Phosphor bronze Admiralty brass

Cupronickel

Molybdenum

Red brass

Brassplating

Yellow brass

Naval brass 464

Uranium 8% Mo

Niobium 1% Zr

Tungsten

Stainless Steel 304 (active)

Tantalum

Chromium plating

Nickel (passive)

Copper

Nickel (active)

Cast iron

Steel

Lead Tin

Indium

Aluminum

Uranium (pure)

Cadmium

Beryllium

Zinc plating

1.9. Batteries:

Batteries are classified into two broad categories, each type with advantages

and disadvantages.

Primary batteries irreversibly (within limits of practicality) transform

chemical energy to electrical energy. When the initial supply of reactants is


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exhausted, energy cannot be readily restored to the battery by electrical

means.

Secondary batteries can be recharged; that is, they can have their chemical

reactions reversed by supplying electrical energy to the cell, restoring their

original composition.

Primary batteries

Primary batteries can produce current immediately on assembly. Disposable

batteries are intended to be used once and discarded. These are most

commonly used in portable devices that have low current drain, are only

used intermittently, or are used well away from an alternative power source,

such as in alarm and communication circuits where other electric power is

only intermittently available. Disposable primary cells cannot be reliably

recharged, since the chemical reactions are not easily reversible and activematerials may not return to their original forms. Battery manufacturers

recommend against attempting recharging primary cells.

Common types of disposable batteries include zinc-carbon batteries and

alkaline batteries. Generally, these have higherenergy densities than

rechargeable batteries, but disposable batteries do not fare well under high-

drain applications with loads under 75 ohms (75 ).

Secondary batteries:

Secondary batteries must be charged before use; they are usually assembled

with active materials in the discharged state. Rechargeable batteries or

secondary cells can be recharged by applying electrical current, which

reverses the chemical reactions that occur during its use. Devices to supply

the appropriate current are called chargers or rechargers.

The oldest form of rechargeable battery is the lead-acid battery. This battery

is notable in that it contains a liquid in an unsealed container, requiring that

the battery be kept upright and the area be well ventilated to ensure safedispersal of the hydrogen gas produced by these batteries during

overcharging. The lead-acid battery is also very heavy for the amount of

electrical energy it can supply. Despite this, its low manufacturing cost and

its high surge current levels make its use common where a large capacity

(over approximately 10Ah) is required or where the weight and ease of

handling are not concerns.


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A common form of the lead-acid battery is the modern car battery, which

can generally deliver a peak current of 450 amperes. An improved type of

liquid electrolyte battery is the sealed valve regulated lead acid (VRLA)

battery, popular in the automotive industry as a replacement for the lead-acid

wet cell. The VRLA battery uses an immobilized sulfuric acid electrolyte,

reducing the chance of leakage and extending shelf life. VRLA batterieshave the electrolyte immobilized, usually by one of two means:

Gel batteries (or "gel cell") contain a semi-solid electrolyte to prevent

spillage.

Absorbed Glass Mat (AGM) batteries absorb the electrolyte in a

special fiberglass matting.

Other portable rechargeable batteries include several "dry cell" types, which

are sealed units and are therefore useful in appliances such as mobile phones

and laptop computers. Cells of this type (in order of increasing powerdensity and cost) include nickel-cadmium (NiCd), nickel-zinc (NiZn), nickel

metal hydride (NiMH) and lithium-ion (Li-ion) cells.[40] By far, Li-ion has

the highest share of the dry cell rechargeable market. Meanwhile, NiMH

has replaced NiCd in most applications due to its higher capacity, but NiCd

remains in use in power tools, two-way radios, and medical equipment.

NiZn is a new technology that is not yet well established commercially.

Recent developments include batteries with embedded functionality such as

USBCELL, with a built-in charger and USB connector within the AAformat, enabling the battery to be charged by plugging into a USB port

without a charger, and low self-discharge (LSD) mix chemistries such as

Hybrio, ReCyko, and Eneloop, where cells are precharged prior to shipping.

1.10 Leadacid battery

Lead-acid batteries, invented in 1859 by FrenchphysicistGaston Plant, are

the oldest type ofrechargeable battery. Despite having a very low energy-to-

weight ratio and a low energy-to-volume ratio, their ability to supply high

surge currents means that the cells maintain a relatively large power-to-weight ratio. These features, along with their low cost, make them attractive

for use in motor vehicles to provide the high current required by automobile

starter motors. In the charged state, each cell contains electrodes of

elemental lead (Pb) and lead(IV) oxide (PbO2) in an electrolyte of

approximately 33.5% v/v (4.2 Molar) sulfuric acid (H2SO4).


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In the discharged state both electrodes turn into lead(II) sulfate (PbSO4) and

the electrolyte loses its dissolved sulfuric acid and becomes primarily water.

Due to the freezing-point depression of water, as the battery discharges and

the concentration of sulfuric acid decreases, the electrolyte is more likely to

freeze during winter weather.

The chemical reactions:

Anode (oxidation):

Cathode (reduction):

Because of the open cells with liquid electrolyte in most lead-acid batteries,

overcharging with high charging voltages generates oxygen and hydrogen

gas by electrolysis of water, forming an explosive mix. The acid electrolyte

is also corrosive.

Practical cells are usually not made with pure lead but have small amounts

of antimony, tin, calcium or selenium alloyed in the plate material to add

strength and simplify manufacture.

Nickel-cadmium battery

The nickel-cadmium battery (commonly abbreviated NiCd or NiCad) is a

type of rechargeable battery using nickel oxide hydroxide and metallic

cadmium as electrodes.

The abbreviation NiCad is a registered trademark of SAFT Corporation,

although this brand name is commonly used to describe all nickel-cadmium

batteries. The abbreviation NiCd is derived from the chemical symbols ofnickel (Ni) and cadmium (Cd).

There are two types of NiCd batteries: sealed and vented. This article mainly

deals with sealed cells.


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