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resistivity of the electrolyte are relatively resistivity of the electrolyte are relatively 2. Secondary reference electrode (Calomel electrode and glass electrode) produced. It is
series, reduction the double
potential layer
increasesof both
and positive
oxidation and
potential negative charges.
decreases. Electrical
Thus this double
series gives the layer
Scanned with CamScanner Electrochemical
increased tendency series
of electrodes to get reduced or decreases tendency of electrodes to get
low. high. Standard Hydrogen Electrode (SHE) corresponds to an electrical capacitor. Electrical properties can be explained qualitatively by
Hg2Cl2 + 2e- →2Hg + 2Cl- oxidised. The electrodes present at the top of the series can function as anode and those present
An the
using electrochemical
concept of series
electrical is double
a series in
aslayer
which
at the the series
Thissolid
electrodes
liquid are arrangedThis
is also interphase.
in the increasing
concept
since was
Reduction occurs at the cathodic area. At the cathodic area, the dissolved constituents in the Electroless plating (Autocatalytic plating) It consists of platinum foil coated with Pt black which is immersed in a solution of 1M at the bottom of the series can function cathode. called activity series,
Zn → Zn2+ + 2e- order
proposed of reduction thepotential
by theatscientist, theor
top of Helmholtz.decreasing order of
He considered oxidation
that potential.
electrical double On moving
layer down the
is produced at
conducting medium accept electrons to form ions like OH -, O2- etc. The non-metallic ions so It is the method of depositing a metal from its salt solution on the catalytically active HCl. Hydrogen gas at 1atm pressure is bubbled over the electrode
the electrodes series is more reactive than those present at the bottom.
The resultant cell can be represented as 2. Secondary reference electrode (Calomel electrode and glass electrode) series,
the reduction
surface of separation Anodic (Active)
potentialbetween
increases theandtwo oxidation
phases, i.e. potential decreases.
the solid electrode Thus
andthis series
liquid gives the
electrolyte.
formed combine with the Mn+ to form corrosion product. The electrons released at the anode surface of the metal to be plated using a2+suitable reducing agent without using electrical energy. Potassium (K)
In this process, metal piece Zn/Zn //KCl(sat)
to be plated /Hg2Cl2(s)/Hg
is immersed /Pt
in a(l)mixture of reducing agent and a Characteristics of SHE Standard Hydrogen Electrode (SHE) Electrical
increased double
tendency layerofconsists
electrodesof twoto parts.
getCalcium
reduced or decreases tendency of electrodes to get
flow through the metal and get consumed in the cathodic reaction, either for the evolution of (Ca)
complex compound. TheE reducing cell = ER – EL =reduces
Ecal – Emetal = 0.2422 - E which 1. Its potential is arbitrarily fixed as zero. electrodes present 1). Fixedtoppart 2)(Na)
Diffused
series canpart
Sodium
hydrogen or for the absorption of oxygen. agent Zn/Zn2+ion into metal Zn/Zn2+gets plated over the It consists of platinum foil coated with Pt black which is immersed inoxidised.
a solutionThe of 1M at the of the
Magnesium (Mg) function as anode and those present
2H+ + 2e- → H2 (g) catalytically active surface ofEthe metal
Zn/Zn2+ = 0.2422 - E cella thin uniformScanned
to produce coating. with
This CamScanner
process is a 2. It is reversible electrode,HCl. i.e. itHydrogen
can function
gas as
at an anode
1atm or cathode
pressure depending
is bubbled onelectrode
over the the nature of Fixed part: It is fixed to the solid electrode.
at the bottom of the series can function Aluminium
It contains
as Zinc
cathode. (Al)either positive or negative ions.
This series is also called activity series, since
½ O2 + H2O + 2e- → 2OH- E cell can be
controlled read directly
chemical from and
reduction volt ismeter.
catalyzed by the metal or alloy being deposited. This the other electrode to which it is connected. Diffused part: It extends some distance into the(Fe)
solution. It contains both positive and negative
(Zn)
the electrodes
ions. The existenceat theof top of the series
charges is more
of opposite reactive
Iron
signs on thethan those to
diffused present at the
the fixed bottom.
part of the electrical
Corrosion with evolution of H2 occurs, when the anodic area is very large and cathodic area is Advantages
method allowsofthe Calomel electrode of films of low thickness using simple equipments. Most
easy preparation If it functions as an anode, it can be represented as Nickel (Ni)
common double layer develops a potential Anodic (Active)
betweenLeads the
Tin two
(Sn) layers. This potential is called electro kinetic
small and it usually occurs in acidic environments. Absorption of O2 occurs in neutral or slightly 1. Itelectroless
is very easy plating
to setisup.
electroless nickel plating. Pt, H2 (g) 1atm / H+ (1M) (Pb)
Electroless Nickel potential or zeta potential. Potassium (K)
alkaline medium. willplating
Hydrogen (H)
2. Its emf not change with chemical reaction. Cell reaction: Scanned with CamScanner Calcium (Ca)
Copper (Cu)
Rusting of iron Pretreatment and activation of the surface
Glass electrode
The surface to be plated is first degreased by using organic solvents or alkali. It is then ½ H2 → H + 1e + - Mercury (Hg)
Sodium
Silver (Ag) (Na)
In this initially a thin film of iron oxide is formed on the surface of iron metal. Some cracks
followed byGlass electrode is a secondary reference
steel electrode. Corning by 015glass hasa been Magnesium
Platinum (Pt)(Mg)
are developed on the iron oxide film. The surface of the metal acts as the anodic area, whereas acid treatment. Surface of stainless is then activated dipping in hot If it functions as a cathode, it can be represented as Gold (Au)
used forofmaking
solution 50% dil.Hglass2SO
electrode.
4. Mg alloy It issurface
a special
cantype of glass with
be activated lowcoating
by thin meltingofpoint
Zn and Copper H+ (1M)/ H2 (g) 1atm, Pt Aluminium
Fluorine (F) (Al)
the interior of the metal behaves as cathode.
and it.
over high electrical
Metals conductivity.
like Cu, Al and alloys It consists ofcan
like brass 72%beSiO 2, 6%Ni
directly CaO & 22%
plated Na2activation.
without O. Non- Cathodic (Noble) Zinc (Zn)
At the anodic area, Fe dissolves as Fe2+ ions with the liberation of electrons. Cell reaction: Hydrogen has zero reduction potential. Above hydrogen, all the electrodes have negative
Construction;
metallic articles like plastics, glasses are activated by dipping them in the solution of SnCl2 and Characteristics of SHE Iron (Fe)
Fe → Fe2+ + 2e- (Oxidation) H+ + 1e -
→ ½ H2 fixed as zero.
reduction potential and below hydrogen, all the electrodes have positive reduction potential.
It consists of a thin glass bulb in which Ag wire coated AgCl is
HCl followed by dipping in PdCl2 solution. A thin layer of Pd will be formed on the surface used as an internal reference 1. Its potential is arbitrarily Nickel (Ni)
Sree Buddha college of Engineering, Pattoor Page 2
The electrons thus released from the anode move to the cathodic area through the metal. These Sree Buddha college of Engineering, Pattoor Page 3
electrode.
upon drying.It is then filled with 0.1N HCl solution. 2. It is reversible electrode, i.e. it can function as an anode or cathode depending on the nature of Tin (Sn)
electrons are then taken up oxygen molecule to form OH- ions. Uses:
Procedure the other electrode to whichCharacteristics
it unknown
is connected. Leads (Pb)
½ O2 + H2O + 2e- → 2OH- It is used for determining potential
of SHE of an electrode.
The pretreated object is immersed in the plating bath containing Nickel sulphate salt Hydrogen (H) Scanned with CamScanner
The Fe2+ ions formed at the anodic area and the OH- ions formed at the cathodic area combine to If it functions
Working as an(Determination
of SHE anode, it1.can be of
represented
Eº using
Its potential as
SHE)
is arbitrarily fixed as zero.
(Coating), hypophosphate reducing agent (Metal deposition), complexing agent like Sodium + Copper (Cu)
form Fe(OH)2 precipitate. Pt,Consider
H2 (g) 1atma/ Zinc rod
H (1M) dipped
2. It in ZnSO4
is reversible solutioni.e.
electrode, of it1Mcanconcentration which
function as an is coupled
anode or cathode depending on the nature of Mercury (Hg)
In the presence of excess of oxygen, Fe(OH) 2 precipitate easily oxidises to get yellow rust having succinate (Quality improvement) and a buffer like Sodium Acetate (P H maintenance). Air is then with reaction:
SHE externally using voltmeter and internally through salt bridge. Now, the resultant cell
applied and heated. Electroless plating of Ni takes place as follows. Cell the other electrode to which it is connected. Silver (Ag)
the formula, Fe2O3.2H2O can be ½ represented
H2 → H+2++as,1e- If+ it functions as an anode, it can be represented as Platinum (Pt)
2Fe(OH)2 + 1�2O2 → Fe2O3.2H2O Zn / Zn (1M)//H (1M)/Pt, H2 (g) 1atm+
SreeBuddha
Sree Buddhacollege
collegeofofEngineering,
Engineering, PattoorPage
Pattoor Page
21 10 If it functions(S)as a cathode, it can be represented
Pt, H2 (g) 1atmas / H (1M) Gold (Au)
If the amount of oxygen is limited, then the corrosion product is black rust (Hydrated magnetite) H+ (1M)/ H2 (g) 1atm, PtCell reaction: Fluorine (F)
3Fe(OH)2 + 1�2O2 → Fe3O4.3H2O Cell reaction: Cathodic (Noble)
½ H2 → H+ + 1e- Hydrogen has zero reduction potential. Above hydrogen, all the electrodes have negative
Galvanic series Ag,AgCl(s)/HCl(0.1N)/Glass// H+ + 1e-→ ½ H2 If it functions as a cathode, it can be represented as
Relative corrosion affinities of metals and alloys can be explained by using a series called reduction potential and below hydrogen, all the electrodes have positive reduction potential.
Glass electrode works on the principle that potential difference between thesurface of the glass H+ (1M)/ H2 (g) 1atm, Pt
galvanic series. This series can be prepared by studying the corrosion affinities of metals and membrane and a solution is a linear function of P H. Here the glass membrane acts as an ion Uses:
alloys in unpolluted sea water without their oxide films. A metal high in this series is more Cell reaction:potential of an electrode. Sree Buddha college of Engineering, Pattoor Page 3
selective membrane sensitive to [H+]. So an ion exchange reaction occurs between singly It is used for determining unknown
anodic and undergoes corrosion faster than the metal below it. The position of a metal in the charged cations of glass (Na+) & H+ ions of solution.Finally an equilibrium is established Working of SHE (Determination of H+Eº+ using
1e-→ ½ H2
SHE)
form of an alloy is different from that of the pure metal in this series. between (Na+) ions of glass & H+ ions of solution. Consider a Zinc rod dipped in ZnSO4 solution of 1M concentration which is coupled
with SHE externally using voltmeter Uses: and internally through salt bridge. Now, the resultant cell
H+(solution) + Na+Gl-→Na+(solution) +H+Gl- It is used for determining unknown potential of an electrode.
Comparison of electrochemical series and galvanic series EG = E0G + 0.0591 log [H+] = E0G - 0.0591 PH E0 Cell =as,E0cathode – E0anode
can be represented
6. Compare the principles
Electrochemical Series of TGA and DTA. (3 Marks) Galvanic series The potential of glass electrode varies with concentration of H + ions. E0G is constant and it Zn(S)/ Zn2+=(1M)//H Working
+0
E0 SHE-E(1M)/Pt,
Zn/Zn2+
ofHSHE (Determination of Eº using SHE)
2 (g) 1atm
Consider a Zinc rod dipped in ZnSO4 solution of 1M concentration which is coupled
Eo is measured only for metals and non- Eo is measured only for metals and alloys. depends on the nature of the glass and also the PH of the solution taken inside the glass bulb. 0.76 V = 0 - E0 with
Zn/Zn2+SHE externally using voltmeter and internally through salt bridge. Now, the resultant cell
metals. TGA Principle DTA Principle E0G= 0.6990 V 0
E Zn/Zn2+
Sree = -0.76Vcan becollege
Buddha representedof 2+ as,
Engineering, Pattoor Page 8
Eo is measured by dipping pure metals in Eo is measured by dipping metals and alloys in The concentration of H+ ion inside the glass is constant,i.e. PH is constant. But when it is dipped +
Eº Cell can be directly read out from the Zn / Zn (1M)//H
(S) voltmeter and (1M)/Pt,
Eº Cathode H2 (g) 1atmHence we can find
is zero.
their 1M salt solution. unpolluted
1. It is a sea water.
thermo analytic technique, used into a solution of unknown PH, concentration of H + ion inside the glass bulb changes. As a result,
1. It is a thermal analytical technique in out EºAnode(EºZn).
SHE is usedthe
which as the referenceand
physical electrode.
chemical Calomel electrode is of
for the identification used as the
different reference
materials PH changes. This results in the development of a potential difference.
like clays, minerals cements etc.
properties of materials are studied as a electrode. Determination of PH using glass electrode Draw backs of SHE
function
Position of of
thetemperature.
metals is fixed. 2. In this
Position method
of the metalthe
andtemperature of the
alloys may change. Glass electrode is used as an internal reference electrode. In order to determine the unknown PH 1. It is very difficult to set up.
It 2.predicts
It is a technique by the mass of It sample
wheredisplacement
the relative predicts and a thermally
the corrosion inert reference
tendencies. of a solution, glass electrode is coupled with SCE and the resultant cell can be represented like 2. It cannot be used as a reference electrode if the solution contains reducible substances such as
a substance is recorded continuously as
tendencies. material are measured as a function of this, Ag,AgCl(S)/0.1N HCl/Glass/Solution of Unknown PH// KCl (sat)/Hg2Cl2(s)/Hg(l)/Pt
the temperature. temperature. copper, silver etc.
0 0
3. This method is used to study several 3. This method is used to study every 3. It causes E Cell = Eof
poisoning cathode E0anode
the Pt– foil.
physical and chemical changes that is chemical and physical changes that Secondary Reference 0
= EElectrode 0
SHE-E Zn/Zn2+
followed by a mass change.. occurs with or without a change in = 0 - E0 Zn/Zn2+
0.76 VReference
Secondary Electrode is a reference electrode with known constant potential
weight.
and can be coupled with other electrodes E0to determine
Cell the–unknown
= E0cathode E0anode potential.
Sree Buddha college of Engineering, Pattoor Page 8
Calomel Electrode = E0 SHE-E0Zn/Zn2+
7. CompareSree
the TGA thermogram
Buddha and DTA thermogram.
college of Engineering, (3 19
Pattoor Page Marks)
0.76 V = 0 - E0 Zn/Zn2+
TGA Thermogram DTA Thermogram Sree Buddha college of Engineering, Pattoor Page 8
Reference holder (R) - To take the reference. calcium oxalate (CaC2O4).The horizontal portion between 226-3460C indicates that anhydrous salt
Temperature sensing device (thermometer) - To note the temperature of the sample. is thermally stable in this range. At slightly above 3460C the anhydrous calcium oxalate
Temperature sensing device (thermometer TR) - To note the temperature of the reference. decomposes to give calcium carbonate. This process is completed at about 4200C. Calcium For More Visit : KtuQbank.com
Environment control equipment - For providing inert atmosphere inside the furnace. carbonate is stable up to 6600C. Above 6600C it decomposes to CaO and CO2. This process is
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Thermal insulation system- To prevent loss of heat. completed at 8400C and above this the horizontal portion represents the stable CaO
Amplifier- To amplify the signals. 4. Explain the TGA curve of polymers. (3 Marks)
Recorder- To record the signal and to graph the thermogram TGA thermogram of some polymers are shown below
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Working
The sample is placed in one chamber and the inert reference material like Al2O3 in the other PVC
PMMA
chamber. The furnace is heated, the difference in temperature between the sample (S) and the M
PE
reference (R). T= TS-TR is continuously measured as a function of the reference sample a PTF
temperature (TR). ss
DTA thermogram
20 30 40 50 60 70
The thermogram obtained is a plot of T= TS-TR versus the reference temperature TR. It is Temperature (0C)
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known as differential thermogram. In the thermogram the upper peak represents the exothermic Thermal analysis and testing of polymers and plastics across the polymer supply chain and
change and lower peak shows the endothermic change occurs in the sample during heating. lifecycle is a powerful means of measuring physical properties, transitions, ageing processes, the
Applications effect of additives and the influence of diverse production conditions on polymer materials.
(i) Identification of substances like clays. 5. Explain DTA of decomposition of hydrated calcium oxalate (5 Marks)
(ii) Used for environmental studies. Differential thermogram of hydrated calcium oxalate in air obtained by increasing the For More Visit : KtuQbank.com
temperature at a rate of 80C/min. It contains two minima (for endothermic process). The single
(iii) DTA is widely used for the quality control of cement glass etc. maxima indicates that oxidation of CaC2O4 to CaCO3 and CO2 is exothermic.
3. Explain the TGA of decomposition of hydrated calcium oxalate (CaC2O4.H2O)
The thermogram of decomposition of pure hydrated calcium oxalate (CaC2O4.H2O) obtained by 2CaC2O42CaCO3+2CO
increasing the temperature at a rate of 50C /min is shown in the figure. Exothermic
The different reactions taking place during heating are 0……………………………………………………………………...
2CaC2O4 2CaCO3+ 2CO (400-5000C) 2CaC2O4 .H2O 2CaC2O4 +H2O 2CaCO3 2CaO+2CO2