Applied Chemistry
Applied Chemistry
Applied Chemistry
LECTURE NOTES ON
APPLIED CHEMISTRY
By
Dr.G.Sujatha
Mr.T.K.Madhusudhan
B.Tech- IISemester L T P C
Branches:- CE, ME & CSE 3 0 0 3
18BS103 APPLIED CHEMISTRY
COURSE OBJECTIVES:
1 To bring adaptability to the concepts of chemistry and to acquire the required skills to become a
perfect engineer.
2 To impart the basic knowledge of atomic, molecular and electronic modifications which makes
the students to understand the technology based on them.
3 To acquire the knowledge of electrochemistry, corrosion and water treatment which are
essential for the Engineers and in industry.
4 To impart the knowledge of stereochemistry and synthetic aspects useful for understanding
reaction pathways.
COURSE OUTCOMES:
At the end of the course students able to
1 The knowledge of atomic, molecular and electronic changes, band theory related to
conductivity.
2 The required skills to get clear concepts on water treatment methods.
3 The required principles and concepts of electrochemistry, corrosion and in understanding the
problem of water and its treatments.
4 The knowledge of configurational and conformational analysis of molecules and reaction
mechanisms.
CHAPTER 2: Water technology-II: water treatment for drinking purpose-disinfection and concept of
break point chlorination –Desalination of brackish water-Principle andProcess of electro-dialysis and
reverse osmosis.
UNIT-IV:
CHAPTER 1:-Stereochemistry:-Introduction to representation of 3-dimensional structures, structural
and stereoisomers, configurations, symmetry and chirality. Enantiomers, diastereomers, optical
activity and absolute configuration...
TEXT BOOKS:
1 Engineering Chemistry by P.C. Jain & M.Jain; Dhanpat Rai Publishing Company (P) Ltd., New
Delhi.
2 University Chemistry, by B.M. Mahan, Pearson IV Edition
3 Engineering Chemistry (NPTEL Web – book), by B.L. Tembe, Kamaluddin and M.S. Krishnan
4. Advanced Physical Chemistry by Gurdepraj
5. Essential Physical chemistry by B.S.Bhal & Arun Bhal and J.D.Tuli , S.Chand Company
6. Organic Spectroscopy by Jag Mohan
7. Engineering chemistry by Sashichawala
REFERENCE BOOKS:
1 Physical Chemistry, by P.W. Atkins
2 Organic Chemistry: Structure and Function by K.P.C. Volhardt and N.E.Schore, 5th Edition.
3. Organic chemistry by Jerry March
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Unit-II
SCIENCE OF CORROSION
INTRODUCTION
The surface of all metals begins to decay when exposed to atmospheric gases, water and
other reactive liquid medium. As a result they are converted to oxides, hydroxides,
carbonates, nitrates, sulphates etc.
Corrosion(oxi)
metal Ore/mineral + Energy
Metallurgy (red)
Reason:-
1. All metals except (Pt, Au, Ag) occurs in a combined state in nature.
2. During extraction of metal from its ore are reduced to metallic compound using energy.
Hence an isolated metal exhibit excited state. However, the metal have natural tendency to
go back to their combined state for its stability. As a result metal exposed to envIronmental
factors where corrosion takes place (conversion of metal to metallic compound).
3. The formation of corrosion is reversible process.
4. It will be measured by units such as mille inches /year or millimeter/year.
Example for corrosion: - A reddish brown layer is formed on to the surface of Iron and
green film on to the surface of copper.
I. Chemical/Dry corrosion
1. Oxidation corrosion.
2. Corrosion by other gases
3. Liquid metal corrosion
1. Oxidation corrosion:-
1. It is brought about by the O2 at low or high temperature on metals, usually in absence
of moisture.
2. At ordinary temperature metals are very shortly attacked, at low temperature alkali (li,
Na, K, Rb etc..) and alkaline earth metals (II group) are rapidly oxidized, at high
temperature all metals except Pt, Au, Ag are oxidized.
3. The reactions in oxidation corrosion are
2M 2Mn++ 2ne- (oxidation by loss of electrons)
n/2O2+ 2ne- nO2- (reduction by gain of electrons)
2M+ n/2 O2 2Mn++nO2-
metal oxide(M2On)
Mechanism: - When oxidation takes place at the surface of metal forms metal oxide scale,
which prevents further oxidation. If oxidation continue either the metal diffuses outwards
through the scale or oxygen diffuses inwards through scale. Both cases can take place but
the outward diffusion of metal is predominantly than inward diffusion of O2. Since the size
of metal is smaller than O2 ion and much higher mobility.
The following types of metal oxide layers are formed by corrosion.
1. Stable: - It is a fine grained layer (film) and tightly adherent to metal surface, hence
this layer doesn’t permit further corrosion.
Eg: Al, Cu, etc.
Me + O2 MO (fine grain layer) no corrosion takes place
2. Unstable: - The metal oxide film is immediately decomposes to metal and O2, hence
further oxidation doesn’t take place.
Eg: Pt, Au, Ag
M+O2 Mo (unstable) no corrosion
3. Volatile:-This type of metal oxide layer is continuously evaporated, hence metal
surface again exposed for further corrosion. This type is seen in Mb (molybdenum)
M+O2 MO (volatile) corrosion takes place
4. Porus: - The resulting metal oxide layer having pores or cracks, through this pores
atmospheric O2 passes into metal surface and hence corrosion continues till the metal
converted to metal oxide.
M+O2 MO (porous) corrosion takes place
Type of metal oxide Example Corrosion
1.stable Cu, Al doesn’t take place
2.unstable Pt, Au, Ag doesn’t take place
3.volatile MO takes place
4. Porous alkali and alkaline earth metals takes place.
The intensity of corrosion decreases due to the formation Gael film which is tightly
adherent on Ag, hence this type is protective.
b. If the film is non- protective or porus : In this case the volume of metal oxide
layer is lesser than that of metal.
Eg: SnCl4 film formed by attack of Cl2 on Sn(tin) which volatiles immediately there by
leaving fresh metal surface for further corrosion.
3. Liquid metal corrosion:-
This is due to chemical action of flowing liquid metal at high temperature on solid metal
or alloy. This type of corrosion is seen in devices used for nuclear plant. The corrosion
reaction is carried out either by dissolution of solid metal or by a liquid metal or internal
penetration of the liquid metal into solid metal. Both corrosion reactions leads to
weakening of solid metal.
Eg: Coolant (Na metal) causes cadmium corrosion in nuclear reactor.
---------------------------------------------------------------------------------------------------
4. The metallic and non-metallic ions diffuse towards each other through conducting
medium and form corrosion product.
a) Evolution of H2:-
This type of corrosion takes place generally in acidic medium when Fe metal is contact
with acidic medium. The anodic reaction is dissolution of Fe as ferrous with liberation of
electrons.
Fe Fe2+ + 2e- (oxidation)
The released electrons from anode flow through metal to cathode where H + ions elevated
as H2.
2H++ 2e _ H2 (reduction)
The overall reaction is
Fe+ 2H+ Fe2+ +H2
This type of corrosion causes displacement of H+ ions by metal ion.(from acidic medium).
All the metals above hydrogen in the electro chemical series have a tendency to get
dissolved in acidic solution with simultaneous liberation of H2 gas.
Absorption of O2:-
When metals are in contact with slightly alkaline or neutral solutions(water) with some
amount of dissolved O2, this type of corrosion takes place .
Ex: Rusting of Iron in neutral aqueous electrolyte solution in the presence of atmospheric
oxygen
The surface of Fe is usually coated with a thin film of iron oxide. However the oxide film
develops cracks, which behave as anodic area and remaining metal part act as cathode. It
shows that anodes are of small area white rest of metallic part forms large area of cathode.
At anode: - Iron dissolves in aqueous solution forms Fe2+ with release of electrons.
Fe Fe2+ + 2e- (oxidation)
At cathode: - The liberated electrons flows from anode to cathode through iron metal,
these electrons are accepted by dissolved O2 to form OH- ions.
½ O2 + H2O + 2 e- 2OH- (reduction)
The Fe2+ at anode and OH- at cathode react to produce ferrous hydroxide precipitate.
Fe2+ + 2 OH- Fe (OH)2
If O2 is available in excess, Fe (OH)2 is easily oxidized to ferrous hydroxide.
4 Fe (OH) 2 + O2 +2H2O 4 Fe (OH) 3 (yellow rust) Fe2O3 xH2O)
If the supply of O2 is limited, the corrosion product may be black anhydrous magnetite
(Fe3O4).
----------------------------------------------------------------------------------------------------
1. Nature of metal
2. Nature of environment
Metal like Ti, Al, Cr, Mg, Ni and CO are passive and they exhibit much higher corrosion
resistance than expected from their positions in galvanic series. Passivity of metal decrease
corrosion rate.
Eg: Corrosion resistance of stainless steel is due to passive character of Cr present in steel.
Viii) Solubility of corrosion product: - In electrochemical corrosion if corrosion
product is soluble in corroding medium, then corrosion proceeds at faster rate. If corrosion
product is insoluble in medium to form another insoluble product which create physical
barrier there by corrosion is suppressed.
Eg: corrosion of Pb in H2SO4 decreases due to formation of insoluble PbSO4.
ix) Volatility of corrosion product :- If corrosion product has volatile nature,
underlined metal is exposed further and cause severe corrosion . Eg: MOO3 is volatile.
--------------------------------------------------
2. Nature of the corroding environment: - The following environmental factors
influence the intensity of corrosion.
1. Temperature. 2. Humidity of air. 3. Presence of impurities in atmosphere. 4. Presence of
suspended particles in atmosphere. 5. Influence of pH. 6. Nature of ions present. 7.
Conductance of conducting medium. 8. Formation of O2 concentrated cell.
1. Temperature: - With increase of temperature of environment, the reaction as well as
diffusion rate increase, there by generally corrosion rate increases.
2. Humidity of air: - It is the deciding factor in atmospheric corrosion. Critical humidity
is defined as the relative humidity above which the atmospheric corrosion rate of metal
increases sharply .The value of critical humidity depends on physical characters of metal
and corrosion product.
In humidity environment the rate of corrosion is higher due to gases and vapours
present in atmosphere furnish (give) water to the electrolyte, essential for setting up of an
electrochemical corrosion cell.
More over the oxide film on metal surface has property to absorb the moisture, so
the corrosion rate enhanced. The nature of moisture sources also play important role.
Eg: Rain water apart from supplying moisture for electrochemical attack, may also wash
away a good part of oxide film from metal surface (unless the oxide film is exceptionally
adherent).
3. Presence of impurities in atmosphere: - Presence of corrosive gases such as SO2,
CO2, H2S, O2 etc in atmosphere increases acidity and increase electrical conductivity which
causes severe corrosion.
In marine atmosphere he presence of Na and other chlorides leads to increase in
conductivity there by corrosion increases.
4. Presence of suspended particles in atmosphere: - The suspended particles in
atmosphere may be are of two types 1) chemically active 2) Chemically inactive. If
suspended particles are active (NaCl, (NH4)2SO4) they absorb moisture and act as strong
electrolytes, thereby causing enhance corrosion.
While suspended particles are chemically inactive, in nature (eg: charcoal) they absorb
both sulphur gas and moisture and slowly enhanced corrosion rate.
5. Influence of PH: - Generally, acidic media (PH<7) are more corrosive than alkaline
and neutral media. The corrosion of metal readily increased by attack of acid, if they can
be reduced by increase of PH of attacking environment.
Eg: Zn rapidly corrodes in Weakley acidic solution of H2Co3 but suffers minimum
corrosion at PH-11.
6. Nature of ions present: - Some of ions increase corrosion while other of the ions
decreases the corrosion. The presence of anions like silicate in medium leads to formation
of insoluble reaction products (silica gel), which inhibit further corrosion. On other hand,
Cl- ions destroy, the protective and passive surface film, hence metal surface get exposed
for fresh corrosion, presence of ammonium salts increase the corrosion of iron. The
presence of even traces of Cu in mine water accelerates corrosion of iron pipes, used for
carrying such water.
7) Conductance of conducting medium: - Conductance of conducting media is
important in case of underground and submerged structures. Corrosion - conductance of
dry sandy soil is lower than those of mineralized/clayey soils. Stray currents (from power
breakages) will cause more severe damage to the metallic structures, burried under clay
and mineralized soil than those under dry sandy soils.
8) Formation of O2 concentrated Cell: - As percentage of O2 increases, the rate of
corrosion also increases due to the formation of O2 concentrated cell. The decay of metal
occurs at the anodic part and cathodic part of metal is protected.
Anodic reaction for Fe: - Fe Fe2+ + 2 e-
Cathodic reaction for Fe: - 2H2O + O2 + 4e- 4OH-
Thus oxidation concentration cell promotes corrosion, but it occurs where O2
concentration is lower.
===============================================================
--------------------===========
Application of Galvanization:
This process is widely used for protection from corrosion of iron or steel in the form of
roofing sheets, wires, pipes, nails, bolts, screws, buckets, tubes etc.
b)Tinning: The process of coating tin over the iron or steel articles to protect them from
undergoing corrosion is known as Tinning. Tin is a noble metal and therefore it possess
more resistance to chemical attack. It is the cathodic protection offered by the tin. In this
process, iron sheet is treated in dilute sulphuric acid (pickling) to remove any oxide film,
if present. A cleaned iron sheet is passed through a bath ZnCl2 molten flux followed by
molten tin and finally through a suitable vegetable oil. The ZnCl2 flux helps the molten
metal to adhere to the base metallic surface. . Palm oil protects the tin coated surface against
oxidation. Tinning of mild steel plates is done mostly for the requirements of the food stuff
industry.
Application of Tinning:
Tinning is widely used for coating of metallic containers for storing foodstuffs, ghee, oils,
kerosene, and packing food materials because of its non-toxic nature.
=======================================================
2. Metal Cladding:
It is the process in which thin layer of coating metal get bonded to base metal on one or
both sides permanently(metal sandwiching) when they are passed through heavy rollers
under the action of heat and pressure.
The choice of cladding metals depends on the corrosion resistance required for any
particular environment. Corrosion resistant metals like Ni,Cu,Pb, Ag, Pt etc., and alloys
like stainless steel, nickel alloys , copper alloys , lead alloys are used as cladding material’s.
In this method the cladding metal is bonded/attached firmly to the base metal.
Advantages:
Metal Cladding gives a very shiny appearance and requires very low maintenance. Once
clad it remains like that for years to come.
Metal Cladding does not absorb any kind of moisture hence it is highly resistant to algae
and fungi.
Metal Claddings are resistant to fire.
Metal Cladding is light in weight and does not increase the dead load of the building.
They are available in a variety of colours and textures.
Metal Cladding provides adequate heat insulation which makes the building energy
efficient and helps in reducing the electricity bills.
Metal is malleable hence can be twisted to any direction so as to create interesting shapes
in the facades.
Metal cladding is very easily available and easy to install.
1Q.CONDUCTANCE:-
= ohm cm
When l = 1cm and
S = 1cm2
R =
R = Resistance in ohms
L = length in cm
S = area of cross – section in cm2
(Rho) = constant, which depends on the mated of the conductor.
The conductance or specific conductance (k) of electrolytic solution is defined as the
reciprocal of its resistance.
1
K
ρ = ohm cm
1
Conductivity K ohm 1cm 1
ohm cm
1000
V K
equivalent wt.
ohm cm 1cm 3
V
equivalentwt.
K = ohm – cm – 1
V = ohm – cm2 equivalents.
b) Molar conductance: The conductance of all ions produced by dissolving one
gram molecular weight of an electrolyte when dissolved in a certain volume ‘v’
ml. which is denoted by the symbol m.
1000 1000
m K V XV V
Molarity of the solution M
cm1 cm3
ohm1
moles
m = ohm – 1 cm2 mole – 1
V
--------------------------------------------------------------------------------------------------------
equation condactanc e of
weak electrolyt e at given concentrat ion( C )
Degree of dissociation () =
equation conductanc e at zero
concentrat ion or infinite dilution (0 )
C
0
The dissociation of water is less and undissociated water may be taken as constant
[H+] [OH -] = constant
The product of the concentration of H+ and OH – expressed in gram moles per lit is
known as Ionic product.
Problem: K = 5.5410 – 8 ohm – 1 cm – 1
conductance (C) = 5.5410 – 8 1000}, lit
C = 5.54 x 0 – 5 ohm – 1 cm2 equ־1
= 349.8 ohm – cm2 equ – 1 = 198.5 ohm – cm2 equ – 1
0 =
C 5.54 105
[OH ] 1.01 10 7
0 548.4
By knowing and K and the volume ‘V’ containing 1gm equivalent can be
determined hence the solubility ‘S’ can be calculated.
1000
S E gm / lit E = equivalent weight of the
V
substance
1000 E K
S Eg: E Agcl = 143.5, = 138.27
1000 143.5 Kv
138.27
4. Basicity of organic acids: After conducting the studies on the sodium salts of a
large number of organic acids Ostwald gave the empirical relation
1024 32
B
10.8
5. Degree of hydrolysis: When a salt of weak acid or base is dissolved in water, the
conductance of solution will be partly due to the ions of the salt and partly due to H+
or OH – ions of the acid or base formed by hydrolysis.
An electrolyte
1
–1
On applying law of mass action; C=
V
.
[ B ][ A ] V V 2
K K Ionization / dissociati on constant
[ BA] 1 (1 )V
V
2
2C 2C
K K
(1 )V (1 ) 1
-------------------------------------------------------------------------------------------------------
Thus, the descending branch of the curve (AB) gives the conductance of a mixture of
acid and salt and the ascending branch of the curve (BC) gives the conductance of a
mixture of salt and excess base.
(b) Titration of strong acid and weak base:-
Ex:- HCl & NH4OH.
When NH4OH is added to HCl, the conductivity decreases due to replacement of H+
ions by NH+4 ions.
H+ Cl- + NH+4OH- NH4Cl- + H2O
After reaching equilibrium the addition of NH4OH after the end point does not
change the conductance because NH4OH, a weakly ionized electrolyte has a very
small conductivity compared with acid or its salt.
(c) Strong base and weak acid:-
The conductance of the acid will below on account of its poor dissociation.
CH3COOH + NaOH Na+ CH3COO- +H2O
When a small amount of NaOH is added to CH3COOH, the conductivity decreases
initially then increases with the further addition of NaOH.
After neutralization, further addition of alkali produces excess of OH -. The
conductance of solution increasing more rapidly.
(d) Weak acid and weak base:- The addition of NH4OH causes decrease in
conductance in the beginning because the common ions formed decrease the
dissociation.
5Q ELECTROCHEMICAL CELLS:-
An electrochemical cell is a device for converting chemical energy into electrical
energy. An electrochemical cell is also commonly referred to as voltaic or galvanic
cell in honour of Volta and Galvane respectively.
In which oxidation occurs at one electrode and reduction at other electrode.
The substances which loses electrons -------oxidized
The substances which gains electrons--------Reduced
In redox chemical reactions, oxidation and reduction takes place at the same time.
Electrochemical cells:-
An electrochemical is a device for converting chemical energy into electrical energy.
A redox reaction is utilized to get electrical energy.
In redox chemical reactions, oxidation and reduction takes place at the same time.
(or)
Electrochemical cell is defined as a single arrangement consisting of 2 electrodes and
capable of producing electricity due to chemical reaction and vice versa.
Galvanic cell:-
The most ideal galvanic cell is Daniel cell. The apparatus that provides electricity
through redox reaction is called galvanic cell, invented by Luigi Galvane (1737-1798)
and also called as voltaic call (Alesandro Volta (1745-1827).
A Galvanic cell is made up of 2 half cell (an individual oxidation and reduction takes
place at 2 electrodes).
On the left Zinc electrode dips into a solution of ZnSO4 (oxidation) and on the right
a Copper electrode dips into a solution of CuSO4 (Reduction).
The 2 electrodes are connected by an external electrical circuit and 2 solutions are
separated by salt bridge. The electrode reactions are:
At anode: Zn Zn2++2e-(oxidation)
At cathode: Cu2++2e- Cu (Reduction)
Zn+Cu2+ Zn2++Cu
This reaction can be readily reversed, because the reaction products, Cd(OH)2 and Ni
(OH)2 adhere to electrode surfaces.
They are mainly used in electronic calculators, CD players, electronic cars, cordless
electronic shavers and transistors. They have long durability without any maintenance.
------------------------------
2.Lithium Batteries: - The cells having lithium anodes are called lithium cells,
irrespective of the cathode used. It is very light metal. It belongs to two categories.
(a) Lithium primary batteries (b) Rechargeable cells / Li+ Ion cells.
a) Li primary cells: The most common Li primary cell is the lithium manganese
dioxide battery.( MnO2)
Anode–Li, Cathode- MnO2, it should be heated, above 3000C to remove H2O before
incorporating it in the cathode. (This step increases the efficiency of cell).
Electrolyte: Mixture of propylene carbonate and dimethoxy ethane containing
dissolved salt such as LiClO4.
Cathode: Li+ + e +Mno2 Li Mno2
Net reaction: Li + Mno2 Li Mno2.
This cells produces a voltage of about + 3.4v, which is more than twice that of dry cell
due to light weight of Li. They are widely used in fully automatic cameras, electronic
devices such as calculators and watches.
--------------------------------
b)Lithium Ion cells or Rechargeable cells:
These cells do not contain metallic Li instead of lithium ion cells are used.
Anode: Carbon compound, graphite (C6)
Cathode: Lithium Cobalt oxide (LiCoO2 )
Electrolyte: LiPF6 or LiBF4
In these cells the true oxidation/ reduction does not takes place instead of that
transport of Li+ ions through the electrolyte from one electrode to the other by the
transport of electrons through the external circuit.
When the cell is constructed, it is in its uncharged state with no Li+ ions between the
layers of ‘c’ atoms in the graphite. When the cell is charging, Li+ ions leave LiCoO2
and travel through the electrolyte to the graphite C6.
LiCoO2 + graphite (C6) Li(1-x) CoO2+ Lix C6.
When the cell is spontaneously discharges to provide electrical power, Li+ ions move
back through the electrolyte to the cobalt oxide while electrons move through the
external circuit from the graphite electrode to the cobalt oxide electrode.
Li1-x CoO2 + LixC6 Li1-x+y CoO2+Lix-yC6
Y=amount of Li+ transferring from LixC6 . LiCoO2 1-x
X= transferring amount of Li+ from LiCoO2 to graphite.
Diagram: see in text book
-----------------------------------------------
III. Fuel cell/Flow battery: - The reactants are continuously supplied from an
external source to the cell and the reaction products continuously removed, such cells
are called as fuel cells. In a fuel cell electrical energy is obtained without combustion
from O2 and gas can be oxidized. Hence fuel cell converts chemical energy of the fuel
directly to electricity.
Fuel + O2 oxidation product + electricity
In which fuel is gas/liquid and oxygen being oxidized. In fuel cell the chemical energy
is provided by fuel and easily converts to electrical energy. Fuel cells are
characterized by,
(1) High efficiency (2) Low noise levels (3) Free from vibration, heat transfer.
The most important fuel cells are
(1) H2-O2 fuel cell (2) Methanol fuel cell
(1)H2-O2 fuel cell/ alkaline fuel cell: - It is successful and simplest cell.
Electrodes: - Porous Platinum electrode, electrolyte -- 35-40% KOH.
It consists of hot concentration KOH electrolyte solution and 2 porous Pt electrodes
are dipped in KOH solution.
At anode H2 gas and at cathode O2 gas is supplied, which are come in contact with
electrodes and shows following reactions.
Cathode: O2 + 2H2O+4e- 4OH- (aq)
Anode : H2+4OH- 4H2O+4e-
H2+O2 2H2O
Applications:
(1) They are used as energy source in space vehicles, submarines or military vehicles.
(2) The reaction product is water, which is harmless and used as source of fresh water
to the astronauts.
(3) The weight of fuel battery for 15 days is about 250 Kg.
Disadvantages:-
(1) Energy cost of generating H2 fuel.
(2) Difficult in storage and distribution of highly flammable.
(3) Availability of alternative fuels.
(2)Methanol fuel cell/proton exchange fuel cells:-
Electrodes:- Porous Pt electrodes, separated by proton transport membrane.
Anode: Oxidation of CH3OH and H2O absorbed on catalyst to from CO2 with lose of
H+ (Protons) and electrons.
Cathode: - H2O is liberated by reduction of O2, which accepts electrons and protons.
Protons are transported from anode to cathode through proton transport membrane,
while electrons transport through electric circuit.
The liberated H2O (at cathode) is consumed at anode.
Oxidation: CH3OH+H2O CO2+6H++6e-
Cathode : 3/2 O2 + 6H++6e- 3H2O
Reaction: CH3OH+3/2 o2 Co2+2H2o
Advantages:-
(1) Storage of methanol is much easier than H2 (does not high pressure or low
temperature) since methanol is liquid form -97.00 C to 64.70 C (-142.60 F to 148.50F)
(2) The energy density of methanol is greater than H2.
Disadvantages:-
(1) During methanol oxidation, CO formed which is strongly adhere on to pt catalyst,
reducing, the surface area and lowering the performance.
(2) CH3OH is toxic and flammable and so utmost care is necessary.
(3) Limited power is produced by them.
Unit-III
INTRODUCTION
Water is one of the most abundant and widely, distributed substance, but is also most
misused one. It covers 3/4 of the earth’s surface and essential for all organisms like
animals, plants, human beings. It is not only essential for organisms but also used in
engineering side for steam generation. In addition to it, water is used for domestic
purposes like drinking, washing, bathing, cooking and used in industries like
production of paper, rayon, textiles, tires, irrigation, atomic energy, steel etc…
2. River water: - Rivers are fed by rain water and spring water. Water from these
sources flow over the surface of earth and dissolves soluble minerals present in the
soil. River water also contain organic matter derived from decomposition of plants
and small particles of sand and rock in suspension i.e. it contain both dissolved and
suspended impurities.
4. Sea water: - It is the most impure form of natural water. All rivers are join in sea
along with their impurities. It contain 3.5% dissolved salts of which 2.6% is NaCl and
other salts are sulphates of Na+, bicarbonates of K+, Mg+2, Ca+2 and bromides of K+
and number of other compounds.
II. Underground water: - The rain water passes down to the lower layers of earth
continuously until it comes in contact with rocks. It comes out of the earth in the form
of spring water.
Well and spring water: - It has high organic purity and consists of more amount of
dissolved salts. It has more hardness.
--------------------------------------------------------------------------------------------------------
--
2Q. IMPURITIES OF WATER:-
Water has following impurities. They are
A. Physical impurities
B. Chemical impurities
C. Biological impurities
A. Physical impurities:-
1. Colour: - Pure water is colourless. Colour to water is caused by the presence
of metallic substances like Fe, Al, humus materials, peats, tannins, algae, fungi,
weeds etc…the change in colour is not harmful unless it comes in contact with
toxic substances.
Eg: Yellow colour presence of Cr and Organic matter
Yellowish red colour presence of Fe
Reddish brown colour presence of peaty matter
B. Chemical impurities:-
Chemical impurities are released from industries, dyes, paints, varnishes etc….
Surface and ground water attains acidity from industrial wastes like acids, mines,
drainage etc… Acidity is caused by the presence of free CO2, mineral salts etc….
Chemical impurities are of three types.
1. Gases:-
a) Dissolved CO2:-All natural water contains dissolved CO2. Its
concentration depends on temperature, pressure and dissolved
mineral content of water. It is acquired from the biological oxidation
of the organic matter. CO2 presence is not significant.
b) Dissolved O2:- Its concentration also depends on temperature,
pressure and content of salts. If it is present in the industrial water it
induces the corrosion. Its presence is necessary to aquatic organism
such as fishes, frogs etc… (for respiration)
c) Dissolved NH3:- It comes from decomposition of nitrogenous
organic matter, sewage containing nitrogenous compounds urea.
These sources converted to NH3.;
2. Organic materials: - These are formed by decaying of micro organism or
decaying of vegetable matter.
3. Inorganic materials: - They are mainly formed due to the soil erosion. They
arise from industrial effluents and rocks. Na+, K+, Mg+2, Ca+2, Mn+2, HCO3-,
CO32, Cl- etc…
Microorganisms: - Abundant in surface water, bur their count is quite low or even
nil in deep well water (Microscope). Commonly microorganisms form slime thereby
causing fouling as well as corrosion. They can grow at 25 0C-35oC which can be
prevented by sterilization (chlorination).
Water bodies: - Bacteria which inhabitation the bottom sludge and planktons
developed at the water surface. These are inhabitated by different group of worms like
flat worms, hair worms, tiny round worms etc…. Most of the worms are parasitic in
nature and harmful to human health and fishes.
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PROBLEMS
Ans
Hard salt Weight(mg/l) Molecular weight CaCO3 Eq.wt/M.wt ×100
Ca(HCO3)2 40.5 162 25
Mg(HCO3)2 46.5 146 31.8
Mg SO4 27.6 120 23
CaCl2 22.4 111 20.18
CaSO4 32.4 136 23.8
N-CH 2 -CH2 -N
EDTA solution: - Dissolve 4 gm of pure EDTA crystals along with 0.1gm of MgCl2
in
1 liter of distilled water.
Indicator: - Dissolve 0.5 gm of EBT in 100ml of alcohol.
Buffer: - Add 67.5 gm of NH4Cl to 570 ml of concentration NH3 solution and make
up with distilled H2O to 1 liter.
Procedure:-
A.Standardization of EDTA:-
1. Rinse and fill the burette with EDTA solution.
2. Pipette out 50ml of standard hard water + 10-15 ml of Ammonia buffer +few drops
Of EBT indicator in conical flask.
3. Titrate with EDTA solution till wine red color changes to clear blue.
Let the volume of EDTA used be V1 ml.
B. Estimation of total hardness :- Take 50ml of given hard water. To this add 10-
15 ml of buffer and few drops of EBT indicator and then titrate with EDTA solution.
Until blue colour is formed.
Let the volume of EDTA used be V2 ml.
8Q.Alkalinity
9Q. Chlorides
10Q.BOILER TROUBLES:-
If hard water is used in boilers the following problems arise boiler. The turbine is a
magnet wounded by coil wire.
1. Priming and foaming
2. Boiler corrosion
3. Formation of scales and sludges
4. Caustic embritllement.
(I)Priming and foaming Or Carry over: - The process of formation of wet steam
is called as priming or carries over. The steam carrying water droplets is called as wet
steam.
(A) Priming: - The phenomenon of steam production along with water droplets by
rapid boiling of water is nothing but priming.
(B) Foaming: - The production of persistent bubbles or foam in boiler water surface
is called foaming.
Prevention:-1. It can be avoided by adding anti-foaming agents like cotton seed oil
and castor oil
2. By adding NaAlO2 which coagulates oily or soapy substances.
Reasons:-
1. Due to presence of dissolved O2...
2. Dissolved CO2.
3. Acids from dissolved salts.
a)Dissolved O2:- At room temperature one liter water consists 8mg of dissolved O2.
It attacks boiler material causing rust formation.
2Fe +2H2O +O2 2Fe (OH)2
4Fe (OH) 2+O2 2(Fe2O3.2H2O)
(Rust)
b). Dissolved CO2:-It gives carbonic acid with water. This carbonic acid has
corrosive effect on boiler material.
H2O + CO2 H2CO3
Carbon dioxide is also produced from decomposition of bi carbonate salts usually
present in water.
Mg (HCO3)2 MgCO3+ H2O +CO2
Removal: - It is removed from water by adding calculated quantity of NH 3 in the
form of NH4OH to produce ammonium carbonate.
2NH4OH + CO2 (NH4)2CO3 +H2O
c). Acids from dissolved salts: - Acids that are produced from dissolved salts are
also mainly responsible for corrosion. Certain salts like magnesium chloride, calcium
chloride etc… produce acids by their hydrolysis.
MgCl2 + 2H2O Mg (OH) 2 +2HCl
The liberated HCl reacts with Fe produces HCl again and finally leads to formation of
rust.
Removal: - It can be removed by neutralizing acids with alkali.
HCl+ NaOH NaCl+ H2O
(iii) Scales and Sludge’s:- In boilers, water evaporates continuously and the
concentration of dissolved salts increase progressively. When their concentration
reach saturation point they are thrown out of water in the form of precipitates on the
surface or inner walls of boilers. The precipitation takes place in two ways.
1. Sludge’s
2. Scales
a). Sludge’s:- 1. Sludge’s are soft, loose, slimy non–stick precipitates produced due
to higher concentrated of dissolved salts.
2. It can easily be scrapped off by wire brush.
Reason: - Sludge’s are formed by substances which have greater solubility’s in hot
water than in cold water.
Eg: MgCl2, Mg (CO3)2, Mg SO4, CaCl2 etc.
Disadvantages:-
1. Sludge’s are bad conductors of heat, hence it wastes portion of heat generated.
2. Excessive sludge formation reduces the efficiency of boiler.
3. It settles in the region of poor circulation areas such as pipe connection, plug
opening, and gauze glass connection leading to checking of the pipes.
Disadvantages:-
1. Wastage of fuel.
2. Decrease in efficiency.
3. Low boiler safety and danger of explosion (at high temperature cracks may
be formed on boilers scale leading to explosion).
4. Scales are bad conductor of heat.
Removal of scales:-
1. Scales are not easily removed by wire brush, scrappers or wiped piece.
2. Scale can be removed by thermal shocks (sudden heating and cooling).
3. Using certain chemicals to removal of scales
a. 5-10% of HCl - used to removal of CaCO3 scales.
b. EDTA- removal of CaSO4 scales.
c. MgO - removal of silica.
4. By adding of anti –coagulants (removal of silica scales).
Water treatment is used for prevention of scales and softening of water. They are two
types.
1. Internal treatment used to remove scales
2. External treatment for softening water.
11Q. Internal treatment: - The following internal conditioning methods are used
for prevention of scales.
12Q. External treatment: - This is used for softening of water. The removal of
hardness causing salts from water is nothing but softening of water. The most
important method for softening is ion exchange process.
Advantages Disadvantages
1. Highly acidic or alkaline water can 1. This equipment is costly.
be treated by this method. 2. More expensive chemicals are
2. It produces very low hardness nearly required for regeneration.
2 ppm. 3. Turbid water cannot be treated by this
3. The softened water is completely free method.
from salts and fit for use in boilers.
Audisankara college of Engineering and technology, Gudur
Dept.of Freshman Engineering
I B.Tech & Sem -II Sub -Applied chemistry Branch: CSE,CE & ME
Question Bank
UNIT-I CHEMICAL BONDING
1. Explain the overlapping of atomic orbitals in the following way
a) Linear combination of atomic orbitals ( 2018/ ECE), ( 2019/ECE)
b) Co axial combination of atomic orbitals
2. Comparision between bonding & anti bonding orbitals ( 2019/ECE)
3. Molecular Energy level diagram (MOELD) for
a) N2 & O2 ( 2018/ ECE)
b) F2 ( 2019/ECE)
4. II- bond /valancy bond theory in
a) 1,3 butadiene, (2019/ECE)
b) benzene
5. Silent features of Crystal field Theory ( 2018/ ECE)
6. CFT in
a) octahedral, (2019/ECE)
b) tetrahedral (2018/ ECE)
c) square planar
UNIT-II ELECTRO CHEMISTRY & CORROSION
1. Explain the Electro chemical cell as Galvanic cell & its representation
2. Conductance & its applications ( 2018/ ECE)
3. Brief account on following types of Batteries
a) NiCad battery
b) Lithium primary battery
c ) Lithium rechargeable battery ( 2018/ ECE) , ( 2019)
4 .Which battery is used as water source for astronauts, explain it. ( 2018/ ECE) , (2019/ECE)
(ans ...H2 & O2 fuel cell)
5. Write about principle , reaction mechanism in methanol- oxygen fuel cell
6. Brief account on Electro chemical corrosion (2019/ECE)
a) Evolution of H2
b) Absorption of O2
7. Write about various Factors influencing the corrosion (2019/ECE)
8. Describe the following for corrosion control
a) Sacrificial anodic protection
b) Impressed current cathodic protection
c) Metal cladding
d) Hot dipping
e) cementation (2019/ECE)
UNIT - III WATER TECHNOLOGY
1. What is Hardness ? write their types
2. What are the units of hardness ? (2019/ECE)
3. Explain the following in Estimation of Hardness by EDTA ( 2018/ ECE) , (2019/ECE)
a) Structure of EDTA b) principle c) procedure d) Calculation
3. Write the following
a) Analysis of water by Winkler’s method / dissolved oxygen
b) Alkalinity c) chlorides
4. Write an essay on Boiler troubles
a) Priming & foaming
b) boiler corrosion ( 2018/ ECE)
c) scales & sludges (2019/ECE)
d) caustic embrittlement (2019/ECE)
5. Ion exchange / demineralization /deioninization of hard water (2019/ECE)
6. Write a short note on Internal treatment or conditioning methods for removal scales
(2019/ECE)
7.Explain the following methods for desalination / demineralization of brackish water or
sea water a) reverse osmosis b) electro dialysis
8. Explain about disinfection methods for treatment of domestic water
(Ozonization & chlorination)
UNIT IV STEREO CHEMISTRY
1. Write an essay on Classification of Isomerism
2. Describe about stereo isomer with examples (2018/ECE)
3. Describe about optical isomer with examples (2019/ECE)
4. 3 D representation of organic molecules (2019/ECE)
5. Describe the conformational analysis in
a) ethane (2018/ECE)
b) n.. Butane
6. Write the differences between Enantiomers & Diastereomers (2019/ECE)
7. Explain about following nomenclature (2019/ECE)
a) D& L nomenclature b) R & S or absolute configuration
UNIT V REACTION MECHANISM
1. Describe the Nucleophilic substitution reaction or SN1 & SN 2 mechanism (2018/ECE) (2019/ECE)
2. Explain about a) Markonikoffs rule (2018/ECE) (2019/ECE)
b)Anti Markonikoffs rule (2018/ECE)
3. Role of Grignard compounds on carbonyl compounds (2018/ECE) (2019/ECE)
4. Write about Nucleophilic addition reactions (2018/ECE)
5. Write about Electrophilic addition reactions .
........................................................................................................................................................
Dr.G.Sujatha