SKSVMACET LAXSHMESHWAR

Department of Chemistry

Mr. J. Yallappa asst professor

Module -04

MODULE 4: Polymers and Green fuels (8hr)

Polymers: Introduction, Molecular weight - Number average, weight average and numerical
problems, Conducting polymers – synthesis and conducting mechanism of polyacetylene and
commercial applications. Preparation, properties, and commercial applications of graphene
oxide. Green fuels: Introduction, construction and working of solar photovoltaic cell,
advantages, and disadvantages. Generation of energy (green hydrogen) from water
electrolysis, advantages, and storage of hydrogen.

Polymers: Introduction, Molecular weight - Number

average, weight average and numerical problems
Polymer introduction:
The word polymer is derived from Greek words, Poly (many) and meros (Parts or unit). A
polymer is a large molecule formed by combining small molecules. The individual small
molecules from which the polymer is formed are known as “Monomers “and the process
bywhich the monomer molecule are linked to form big polymer molecule is called
“polymerization”
Polymerization
nCH2=CH2 → -(CH2-CH2-)n
Ethylene Polyethylene
The length of the polymer chain is specified by the number of repeat unit in the chain,
theaverage number of repeat units in the chain is called “degree of polymerization” (n).
The polymers are generally called as “Plastics”
Polymerization is a process which allow monomer to combine and form polymer. The
numberof reactive site (bonding) available in a molecule for a particular reaction is called
“functionality”. Ethylene has functionality of two, acetylene has functionality of four.

Types of Polymers

There are many types of polymers including synthetic and natural polymers.

Natural biopolymers
Polypeptides in proteins - silk, collagen, keratin.
Polysaccharides (Carbohydrate chains) - cellulose, starch, glycogen
Nucleic acids - DNA and RNA

Synthetic polymers

Plastics
Elastomers - solids with rubber-like qualities
o Rubber (carbon backbone often from hydrocarbon monomers)
o silicones (backbone of alternating silicon and oxygen atoms).
Fibers
Solid materials of intermediate characteristics
Gels or viscous

liquidsClassification of

Polymers

Homopolymers: These consist of chains with identical bonding linkages to each

monomer unit. This usually implies that the polymer is made from all identical monomer
molecules.These may be represented as : -[A-A-A-A-A-A]- Homopolymers are
commonly named by placing the prefix poly in front of the constituent monomer
name. For example, polystyrene is the name for the polymer made from the monomer
styrene (vinylbenzene).
Copolymers: These consist of chains with two or more linkages usually implying two or
more different types of monomer units. These may be represented as : -[A-B-A-B-A-B]-

Polymers classified by mode of polymerization

Addition Polymers: The monomer molecules bond to each other without the loss of
anyother atoms. Addition polymers from alkene monomers or substituted alkene
monomers
 are the biggest groups of polymers in this class. Ring opening polymerization can occur
without the loss of any small molecules.
Condensation Polymers: Usually two different monomer combine with the loss of a
smallmolecule, usually water. Most polyesters and polyamides (nylon) are in this class
of polymers. Polyurethane Foam in graphic above.

Molecular weight - Number average, weight average and numerical problems of polymer
and numerical problem.

Molecular weight of polymer

(a) In contract to the low molecular weight compound, polymer is usually a complex
mixture of molecules of different molecular weights. The polymer are thus
polydisperse and heterogeneous in composition. Therefore the molecular weight of a
polymer is actually an average of the molecular weights of constituent molecules.
(b) Different averages are obtained depending on the method of measurement of the
molecular weight.
(c) The number average molecular weight Mn is obtained by the measurement of the
colligative properties of a polymer by Osometry or end group analysis and is defined as

Mn= ∑Ni.Mi/∑Ni

Where Ni is the number of molecules of molecular weight Mi

The weight average (MW) molecular weight is obtained from light scattering measurement
and is defined as
Mw= ∑Ni.Mi2/∑Ni.Mi

To explain these molecular weight averages

Example Suppose there are 50 polymer molecules of molecular weight 102, 200 polymer
molecules of molecular weight 103, and 100 molecules of molecular weight 104. Then

Mn= 50X102+200X 103+ 100X104/ 50+200+100

= 3443 approx.
Mn= 50X104+200X106+100X108/ 50X104+200X103+100X104
=8470 approx.

Numerical problem 1
1. A polymer has the following composition 100 molecular mass 1000g/mol, 200
molecules of molecular mass 2000g/mol and 500molecular mass
5000g/mol.Calculate the number and weight average molecular weight.
Solution :
Given M1=1000g/mol, N1=100: M2= 2000g/mol : N2= 200, M3= 5000g/mol, N3= 500
The number average molecular weight in given by
Mn= ∑Ni.Mi/∑Ni
= 100X1000+200X2000+500X5000/ 100+200+500
=1X105+4X105+25X105/800
=3.75X103 g/mol
The weight average molecular weight is
Mw= ∑Ni.Mi2/∑Ni.Mi
=100X10002+200X20002+500X5002/30X105
= 1X108+8X108+125X108/30X105
=4.46X103g/mol

Conducting polymers – synthesis and conducting mechanism of

polyacetylene.
Definition conducting polymer

Organic polymers that conduct electricity are known as conducting polymers.

They are also known as intrinsically conducting polymers (ICPs) and they have
alternating single and double bonds along the polymer backbone (conjugated bonds)
or
 that are composed of aromatic rings such as Phenylene, naphthalene,
anthracene,pyrrole, and thiophene which are connected through carbon-carbon
single bonds.

Examples: Polyacetylene, Polypyrrole, Polyaniline, etc

Synthesis of polyacetylene
A variety of methods have been developed to synthesize polyacetylene, from pure
acetylene and other monomers.
One of the most common methods uses a Ziegler–Natta catalyst, such
as Et3Al/Ti(OC3H7)4, with gaseous acetylene. This method allows control over the
structure and properties of the final polymer by varying temperature and catalyst.

Mechanism of polyacetylene:
(a) Polyacetylene consists of hundreds to thousands of carbon atoms linked by alternating
single and double bond. Conductivity of pure oxyacetylene is about 4.4X10-5S/cm.
(b) Upon doping with oxidizing agent like iodine, the conductivity increases to about 400
S/cm
(c) When the oxidative dopart such as iodine is added, it takes away an electrons from the ∏
-back bone of the pollyacetylene chain and creates a positive centre (hole) on one of the
carbon.
(d) The other ∏- electron resides on the other carbon making it a radical. The radical ion
formed is called Polaron. A dipolar on (soliton) is formed on further oxidation.
(e) These radicals migrate and combine to establish a backbone double bond. As the two
electrons are removed, the chain will have two positive centre (holes).
(f) The chain as a whole is neutral, but holes are mobile and when a potential is applied the
migrate from one chain as a whole is neutral but holes are mobile and when a potential is
applied they migrate from one carbon to another and account for conductivity. This
depicted by the sequence of reaction.
(g) When a ∏- bond is formed, valence (VB) and conduction bond (CB) are created. Before
doping there is sufficient energy gap between VB and CB, so the electron remain VB and the
polymer acts as an insulator.
(h)Upon doping polarons and Solitons are formed which results in the creation of new
localized electronic states that fill the energy gap between VB and CB.When sufficient soliton
are formed, new mid gap energy band created which overlaps with valence and conduction
bands allowing electrons to flow.
Application polyacetylene conducting polymer.
The most extensively studied and is widely investigated computationally and experimentally
for use in electronic devices such as light-emitting diodes, water purification devices,
hydrogenstorage, and biosensors.

Graphene Oxide:
 Graphene oxide (GO) is a layered carbon structure with oxygen-containing functional
groups (=O, -OH, -O-, -COOH) attached to both sides of the layer as well as the edges of
the plane.
 As with any 2D carbon material, GO can also have either single layer or multilayer
structure.
 A structure with one layer is graphene oxide; two layers of graphene oxide are referred
to as a two-layered GO, GO with five to ten layers is called multi layered GO, and
materialwith eleven or more layers is called graphite oxide.
 In contrary to graphene, GO is hydrophilic, and it is hence relatively simple to prepare
a water- or organic solvent-based suspensions.
 Highly oxidized forms of GO are electric insulators with a bandgap of approximately 2.2
eV.

 Simplistically, GO is a monolayer sheet of graphite containing hydroxyl, carboxyl, and

epoxy oxygen groups on its basal plane and edges, resulting in a mixture of sp2 and
sp3 hybridized carbon atoms.
Properties of GO:
 The properties of graphene can be changed by the functionalization of graphene
oxide.The chemically-altered graphene’s could possibly be used in several applications.
 Graphene Oxide has a high surface area, and so it can be fit for use as electrode
materialfor batteries, capacitors and solar cells.
 Graphene Oxide is cheaper and easier to manufacture than graphene, and so may
entermass production and use sooner.
 GO can easily be mixed with different polymers and other materials, and
enhanceproperties of composite materials like tensile strength, elasticity, conductivity
and more.
Synthesis of grapheme oxide ( Hammer method)
 There are several ways to prepare graphite oxide/graphene oxide. The most common
wayis to use an oxidizing agent in an acidic environment.
 In this procedure, phosphoric acid is mixed with sulphuric acid in the ratio 1:9
andpotassium permanganate and graphite added in the ratio 6:1 in an ice bath
(Figure 3A).

Graphene oxide
synthesis

 The mixture is then heated at 50oC and stirred for 12 h (Figure 3B). After cooling
down, the mixture is poured onto ice (Figure 3C).
 Finally, 30% H2O2 is added in order to remove the excess of potassium
permanganate(Figure 3D).
 Phosphoric acid works as a dispersive and etching agent, as well as a stabilizer of
theoxidation process, which makes the synthesis of GO safe.
 This route produces a higher yield of GO with a higher level of oxidation and a
moreregular structure.

Applications of graphene oxide

1. Environmental Applications of GO
 Air pollution caused by the industrial release of harmful gases such as CO2, CO,
NO2,and NH3.
 GO can be employed in catalysis for converting polluting gases during industrial
processing.
 The approach of GO application in this area can be divided into two paths:
pollutantadsorption and conversion.
Removal of Toxic Gases
  The functional groups of few-layered GO composites exhibit unique adsorption
behaviour towards different gases like acetone, formaldehyde, H2S, SO2, and NOx can be
adsorbed by GO-based composites.
Water Purification
 GO exhibits high adsorption ability towards Cd(II), Co(II), Au(III), Pd(II), Ga(III), and
Pt(IV).
 Adsorption ability mainly depends on the synthesizing method. Multi-layered graphene
oxide nanosheets show a very high affinity towards Pb(II) ions, with a sorption capacity
of about 842 mg g-1 at 293 K.
Medical and Biological Applications of GO
 Small-molecule drug delivery seems to be another promising medical application of
GO.Small molecules of drugs can be attached to a GO surface using pH-sensitive
linkers.
 More over cancer targeting was successfully manifested as a codelivery
ofcamptothecin (CPT) using folic acid conjugated nano GO (FANGO).

Green Chemistry and alternative energy resources

Introduction:

 Prevents pollution at the molecular level

 Is a philosophy that applies to all areas of chemistry, not a single discipline of
chemistry
 Applies innovative scientific solutions to real-world environmental problems
 Results in source reduction because it prevents the generation of pollution
 Reduces the negative impacts of chemical products and processes on human health
and the environment
  Lessens and sometimes eliminates hazard from existing products and processes
 Designs chemical products and processes to reduce their intrinsic hazard

Green chemistry Definition

Green chemistry is the design of chemical products and processes that reduce or eliminate
the use or generation of hazardous substances. Green chemistry applies across the life cycle
of a chemical product, including its design, manufacture, use, and ultimate disposal. Green
chemistry is also known as sustainable chemistry.

Green chemistry's 12 principles

These principles demonstrate the breadth of the concept of green chemistry:

1. Prevent waste: Design chemical syntheses to prevent waste. Leave no waste to treat or
clean up.

2. Maximize atom economy: Design syntheses so that the final product contains the
maximum proportion of the starting materials. Waste few or no atoms.

3. Design less hazardous chemical syntheses: Design syntheses to use and generate
substances with little or no toxicity to either humans or the environment.

4. Design safer chemicals and products: Design chemical products that are fully effective yet
have little or no toxicity.

5. Use safer solvents and reaction conditions: Avoid using solvents, separation agents, or other
auxiliary chemicals. If you must use these chemicals, use safer ones.

6. Increase energy efficiency: Run chemical reactions at room temperature and pressure
whenever possible.
7. Use renewable feedstock’s: Use starting materials (also known as feedstock’s) that are
renewable rather than depletable. The source of renewable feedstocks is often agricultural
products or the wastes of other
 processes; the source of depletable feedstocks is often fossil fuels (petroleum, natural gas, or
coal) or mining operations.

8. Avoid chemical derivatives: Avoid using blocking or protecting groups or any temporary
modifications if possible. Derivatives use additional reagents and generate waste.

9. Use catalysts, not stoichiometric reagents: Minimize waste by using catalytic reactions.
Catalysts are effective in small amounts and can carry out a single reaction many times.
They are preferable to stoichiometric reagents, which are used in excess and carry out a
reaction only once.

10. Design chemicals and products to degrade after use: Design chemical products to
break down to innocuous substances after use so that they do not accumulate in the
environment.

11. Analyze in real time to prevent pollution: Include in-process, real-time monitoring and
control during syntheses to minimize or eliminate the formation of byproducts.
Solar Energy
Photo-voltaic cells:
Photovoltaic cells or solar cells are semiconductor devices that convert sunlight into direct
current. As long as light is shining on the solar cell it generates electrical power. When the
light stops electricity stops.
Construction and working of photovoltaic cell Construction
1. Atypical silicon photovoltaic cell is composing of a thin wafer consisting of an ultra-thin layer
of Phosphorous doped (n-type) silicon on the top and boron doped (p-type) silicon at the
bottom.
2. Hence a p-n junction is formed between the two.
3. A metallic grid above the diode forms one of the electrical contacts and allows the light to
fall on the semiconductor.
4. The anti-reflexive layer (Silicon nitride or TiO2) present in between the metallic grid increases
the transformation of sunlight to a semiconductor. The other metallic layer at the back of the
semiconductor forms another electrical contact.
 Working
1. Electromagnetic radiation consists of photon. The photon carries a certain amount of energy.
It is given by the Planck Constant equation is
E=hc/λ where h is called Planck constant C is the velocity of light and λ is wavelength of the
radiation.
When the electromagnetic radiation falls on the p-n junction diode, electron pair hole is
generated. Electrons move and collect at the n-type end and the holes moves towards the p-
type end, on connecting these two ends trough conductor flows between them to an
external circuit.
Diagram 4: PV / Solar cell
Application
1. For producing electricity using solar power plants
2. To provide electricity to satellites.
3. In remote sensing techniques from space using satellites with objectives.
4. To provide reliable weather monitoring and forecasting, there by
monitoring the climatic factors.
High energy fuels: Production of hydrogen (water electrolysis), advantages and storage of
hydrogen.

(a) Electrolysis is a promising option for carbon-free hydrogen production from

renewable and nuclear resources.
(b) Electrolysis is the process of using electricity to split water into hydrogen and oxygen.
(c) This reaction takes place in a unit called an electrolyzer. Electrolyzers can range in
size from small, appliance-size equipment that is well-suited for small-scale
distributed hydrogen production to large-scale, central production facilities that
could be tied directly to renewable or other non-greenhouse-gas-emitting forms of
electricity production.
Construction

(a) Like fuel cells, electrolyzers consist of an anode and a cathode separated by an
electrolyte. Different electrolyzers function in different ways, mainly due to the
different type of electrolyte material involved and the ionic species it conducts.
(b) Polymer Electrolyte Membrane Electrolyzers.In a polymer electrolyte
membrane (PEM) electrolyzer, the electrolyte is a solid specialty plastic
material.

 Water reacts at the anode to form oxygen and positively charged hydrogen ions
(protons).
 The electrons flow through an external circuit and the hydrogen ions selectively
move across the PEM to the cathode.
 At the cathode, hydrogen ions combine with electrons from the external circuit to
form hydrogen gas.
 Anode Reaction: 2H2O → O2 + 4H+ + 4e-
 Cathode Reaction: 4H+ + 4e- → 2H2
(a) Alkaline Electrolyzers

1. Alkaline electrolyzers operate via transport of hydroxide ions (OH-) through the electrolyte
from the cathode to the anode with hydrogen being generated on the cathode side.

2. Electrolyzers using a liquid alkaline solution of sodium or potassium hydroxide as the

electrolyte have been commercially available for many years.

3. Newer approaches using solid alkaline exchange membranes (AEM) as the electrolyte are
showing promise on the lab scale.

(c) Solid Oxide Electrolyzers

Solid oxide electrolyzers, which use a solid ceramic material as the electrolyte that selectively
conducts negatively charged oxygen ions (O2-) at elevated temperatures, generate hydrogen
in a slightly different way.

 Steam at the cathode combines with electrons from the external circuit to form
hydrogen gas and negatively charged oxygen ions.
 The oxygen ions pass through the solid ceramic membrane and react at the anode to
form oxygen gas and generate electrons for the external circuit.

Solid oxide electrolyzers must operate at temperatures high enough for the solid oxide
membranes to function properly (about 700°–800°C, compared to PEM electrolyzers, which
operate at 70°–90°C, and commercial alkaline electrolyzers, which typically operate at less
than 100°C).

Advanced lab-scale solid oxide electrolyzers based on proton-conducting ceramic electrolytes

are showing promise for lowering the operating temperature to 500°–600°C. The solid oxide
electrolyzers can effectively use heat available at these elevated temperatures (from various
sources, including nuclear energy) to decrease the amount of electrical energy needed to
produce hydrogen from water.
 Potential for synergy with renewable energy power generation(advantages)
(a) Hydrogen production via electrolysis may offer opportunities for synergy with
dynamic and intermittent power generation, which is characteristic of some
renewable energy technologies.

(b) Today's grid electricity is not the ideal source of electricity for electrolysis
because most of the electricity is generated using technologies that result in
greenhouse gas emissions and are energy intensive.
(c) The cost of renewable-based electricity production and develop more
efficient fossil-fuel-based electricity production with carbon capture,
utilization, and storage.
(d) Research Focuses On Overcoming Challenges
Disdavantages
 Durability trade-offs of electrolyzer systems under predicted future
dynamic operating modes using CO2-free electricity.
 Reducing the capital cost of the electrolyzer unit and the balance of
the system.
 Improving energy efficiency for converting electricity to hydrogen
over a wide range of operating conditions.
 Increasing understanding of electrolyzer cell and stack degradation
processes and developing mitigation strategies to increase
operational life.
Hydrogen storage
 Hydrogen can be stored physically as either a gas or a liquid. Storage of
hydrogen as a gas typically requires high-pressure tanks (350–700 bar
[5,000–10,000 psi] tank pressure).
 Storage of hydrogen as a liquid requires cryogenic temperatures because
the boiling point of hydrogen at one atmosphere pressure is −252.8°C.
 Hydrogen can also be stored on the surfaces of solids (by adsorption) or
within solids (by absorption).