BMS College Engineering, Bengaluru 560 019

(An Autonomous College under VTU)

Department of Chemistry
Unit 3. Energy – Conversion and Storage
a. Chemical fuels
 Classification of fuel, units of heat.
 Calorific value - gross & net calorific values – definition, calculation of heat associated with steam.
 Determination of calorific value of a solid / liquid fuel using Bomb calorimeter – principle, figure,
procedure & calculation, water equivalent of calorimeter, numerical problems on calorific value.
 Petroleum cracking - purpose of cracking, fluidized bed catalytic cracking (figure, explanation & ex.)
 Reformation of petrol – definition, catalytic reformation, 4 reactions with conditions.
 Octane number – definition.
 Synthetic petrol - Fischer-Tropsch's process (figure, explanation & reactions).
 Power alcohol – definition, advantage & disadvantage.
 Biodiesel - definition, trans-esterification - process with reaction, advantage & disadvantage.
 Hydrogen as a fuel – production, storage, advantage & disadvantage.
b. Photovoltaic cells
 Physical & chemical properties of silicon relevant to photovoltaics.
 Production of solar grade silicon – metallurgical grade, refining, zone refining & Czochralski’s
crystal pulling technique.
 Doping of silicon – diffusion & ion implantation technique.
 Construction & working of a PV cell & uses.
c. Batteries
 Basic concepts – components of battery.
 Battery characteristics – EMF, capacity, current, storage density, power density, cycle life, energy
efficiency, shelf life.
 Classification of batteries – primary & secondary batteries.
 Modern batteries - construction, working & applications of -
 Zinc-air battery (figure, explanation, anodic & cathodic materials reactions and use)
 Nickel-metal hydride battery (figure, explanation, anodic, cathodic materials, reactions & use)
 Li-ion batteries battery (figure, explanation, anodic, cathodic materials, reactions & use)
d. Fuel cells
 Introduction
 Differences between battery & fuel cell
 Construction & working of methanol-oxygen fuel cell (figure, explanation, anode, cathode, reactions
& use)

1 Dr. AN, Dept. of Chemistry, BMS CE (2018-19 – I, for CJ and CE)

Czochralski’s crystal pulling technique
A polycrystalline silicon contains large number of crystals oriented randomly Because of this their
properties are not uniform. Solid state devices such as transistors, integrated chips (IC’s) require single
crystal of high purity. One of the widely used methods of obtaining single crystal is Czochralski’s crystal
pulling technique.
Czochralski’s technique is a process of growing
a single crystal from the melt of the compound
on a seed crystal. Pure silicon is taken in a quartz
lined graphite crucible and melted in an
atmosphere of argon. Properly oriented single
crystal of silicon attached to a puller rod is
lowered into the melt. It is rotated and pulled out
slowly at a speed of 1.5 – 5 cm per hour. The
atoms from the melt reproduce same atomic
arrangement as that of the seed crystal. This gives a big single crystal. Single crystals of length 0.5 – 1 m
have been grown by this technique.

2 Dr. AN, Dept. of Chemistry, BMS CE (2018-19 – I, for CJ and CE)

Unit 4. Polymer Chemistry: (for Test 2)

Introduction Degree of polymerization, Tacticity.

mechanism of coordination polymerization (Zeigler-Natta polymerization) – propene as example.

methods of polymerization – bulk, solution, suspension and emulsion polymerization – compare all

methods, advantage and limitations.

number average molecular weight, weight average molecular weight and their determination numerical

problems.

Coordination polymerization
Polymerization reactions of olefins and dienes catalyzed by organometallic compounds are termed
coordination polymerization. In coordination polymerization, usually transition-metal catalysts are used.
An example for this is Ziegler-Natta catalyst. This catalyst consists of trivalent aluminium, AlEt3 and
tetravalent titanium, TiCl4 combination as below. It is a subclass of addition polymerization.
Zeigler-Natta catalysts: These are catalysts generally having two components, catalyst and a co-
catalyst. The catalyst is titanium tetrachloride (TiCl4) and the co-catalysts can be organo-aluminium
compounds such as triethyl aluminium (AlEt3) or diethyl aluminium chloride (AlEt2Cl). Alkyl
aluminiums act as the electron acceptor, whereas the electron donor is titanium tetrachloride and the
combination, therefore, readily forms coordination complexes. The complex formed is insoluble in the
solvent and hence heterogeneous in nature.

A growing polymer chain is coordinatively bonded to a metal atom with vacant d-orbitals. A new
monomer molecule is inserted by the creation of bonds between one of its carbon atoms and the metal
and between the other carbon atom and the innermost carbon atom of the existing chain. Branching will
not occur through this mechanism since no radicals are involved; the active site of the growing chain is
the carbon atom directly bonded to the metal. High density polyethene (HDPE) is produced by this type
of polymerization. The most important catalyst for coordination polymerization is Ziegler-Natta
catalysts, effective for alkene polymerization. An important property of these catalysts is that they yield
stereo-regular polymers, e.g. polymerization of propene produces polypropene with high stereo-
regularity.

3 Dr. AN, Dept. of Chemistry, BMS CE (2018-19 – I, for CJ and CE)

The polymerization using propene as substrate follows three steps,
(a) Initiation: The vacant d orbital in active catalyst (shown above) forms π-complex with monomer
propene.

(b) Propagation: Repeating above sequence, addition of a second monomer molecule, the resulting
chain grows as follows,

The chain grows by monomeric insertion at the titanium-carbon bond.

(c) Termination: It can occur by any of the following three mechanisms,
(i) Termination by chain transfer to monomer

(ii) Termination by internal transfer – internal hydride transfer

(iii) Termination by an active hydrogen compound

Advantages of coordination polymerization

1. ‘Living’ polymerization - Chain terminus (termination by internal hydride transfer and chain transfer
to monomer) being olefin, polymer remains active even after all monomers are used up. (Living
polymer: A polymer having reactive double bond at the end of polymer chain).
4 Dr. AN, Dept. of Chemistry, BMS CE (2018-19 – I, for CJ and CE)
2. Heterogeneous (solid-phase) metal catalyst, easy recovery, recycled catalyst
3. High density (linear polymers and isotactic polymers) with minimal branching are obtained

Classification based on the stereo-regularity

5 Dr. AN, Dept. of Chemistry, BMS CE (2018-19 – I, for CJ and CE)

For Unit 5 (not required for Test 2)
Single walled CNT

Multi walled CNT

C60

6 Dr. AN, Dept. of Chemistry, BMS CE (2018-19 – I, for CJ and CE)