Engineering Chemistry: Module - 1

Engineering Chemistry
Module -1
A) Laws of thermodynamics - entropy change (selected
processes) – spontaneity of a chemical reaction and Gibbs free
energy - heat transfer;
B) Kinetics - Concept of activation energy and energy barrier -
Arrhenius equation- effect of catalysts (homo and
heterogeneous) – Enzyme catalysis (Michaelis-Menten
Mechanism).
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1st class 5th class
Thermodynamics: Basic Terminologies Chemical kinetics
0th Law of Thermodynamics Factors affecting reaction rates
1st Law of Thermodynamics Rate laws and rate constants
First order reaction
2nd class Half-life of first order reaction
Enthalpy & Heat Capacity 6th class
Application of 1st Law to the Expansion Work Second-order reactions
Numerical from 1st Law Zero-order reactions
Pseudo first order reaction
3rd class 7th class
2nd Law of Thermodynamics Temperature and rate of reactions
Entropy and Carnot Cycle Collision model and activation energy
Arrhenius equation
4th class Catalysis
Free Energy 8th class
Numerical from 2nd law of Thermodynamics Types of catalysis
Spontaneity of a Chemical Reaction Homogeneous and Heterogeneous catalysis
3rd Law of Thermodynamics Enzyme catalysis
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Michaelis-Menten equation
Part-A
Thermodynamics
- Laws of thermodynamics
- entropy change (selected processes)
– spontaneity of a chemical reaction and
- Gibbs free energy - heat transfer
3
Thermodynamics: Basic Terminologies
the quantity of matter or a Properties of a system:

Thermodynamic Systems: region in space upon which # Intensive Properties:
attention is concentrated in the
analysis of a problem
Everything
external to
the system
# Extensive
Properties
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Internal energy (U)

# State function: = Kinetic energy + Potential energy
Depends on the initial state & final state;
independent of the path used to reach from. ∙ It’s a state function & an extensive property
Example: T (Temperature), P (Pressure), U of the system.
(Internal energy), H (Enthalpy) etc. ∙ Internal energy of a system changes when
energy is transferred into or outside the
system in the form of heat or work
# Path function:
Depends on the path between the initial & final
state 5
Example: W (work done), q (heat transferred) etc.
State of a system
⮚ The state of thermodynamic variables Work done on/by the system
such as pressure, temperature, volume, W (Work) = F (force) x w (distance moved in the direction of
composition which describes the system force)
is called state of the system.
⮚ when one/more variables undergo
change, the system is said to have
undergone a change of state
• Adiabatic – no heat transferred
• Isothermal – constant
temperature
• Isobaric – constant pressure
• Isochoric – constant volume
⮚ Gas is heated ⇒ it will expand and pushes the piston, thereby doing work on the piston.
The work done (dw) when the system expands by dV against a pressure Pex:
dw = −PexdV
� This is an example of the system doing the work on the surrounding 6

Reversible Process in Thermodynamics
# Example 1:
❑ A thermodynamic process is
Thermal equilibrium of two systems with the same temp.
reversible if the process can be
▪ If the temperature of either system is lowered infinitesimally,
turned back such that both the
then energy flows into the system with the lower temperature.
system and the surroundings
▪ If the temperature of either system at thermal equilibrium is
return to their original states,
raised infinitesimally, then energy flows out of the hotter system
with no other change anywhere
else in the universe.
# Example 2:
❑ In reality, no such processes as Reversible expansion:
reversible processes can exist. Suppose a gas is confined by a piston.
external pressure (Pex) = pressure (P) of the confined gas.
❑ A change can be reversed by ▪ Such a system is in mechanical equilibrium with its
an infinitesimal modification of surroundings because an infinitesimal change in the
a variable. external pressure in either direction causes changes in
volume in the opposite directions.
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0th Law of Thermodynamics
⮚ According to 0th law:

If two systems are in thermal equilibrium with a third
system, then those two systems are in thermal
equilibrium with each other.
❑ Two physical systems are in

thermal equilibrium if there is no
net flow of heat (thermal energy)
between them when they are
connected by a path permeable to
heat.
⮚ The 0th law of thermodynamics defines thermal equilibrium

and forms a basis for the definition of temperature.
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1st Law of Thermodynamics
▪ It’s the law of conservation of energy

❑ The energy of an isolated system remains constant. Whenever a quantity of energy (some
form) disappears, an exactly equivalent quantity of energy (some other form) must make an
appearance.
⮚ Heat (q) and work (w) are equivalent ways of changing the internal energy of a system
→ Example:
o If a weight has been raised/lowered in the surroundings, transfer of energy happens by doing the
work.
o If ice melts in the surroundings, it indicates the transfer of energy as heat.
⮚ For a system, if w = work done on a system, q = energy transferred as heat to a system & ΔU =
resulting change in internal energy
The signs of w and q:
✔ +ve if energy is transferred to the system as work/heat
✔ -ve if energy is lost from the system.
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Enthalpy & Heat Capacity
⮚ If the change of a system is brought ❑ Heat capacity (C) of a system b/n any two
about at constant pressure, there will be temperatures – the quantity of heat (q) required to
change in volume. raise the temperature of the system from the lower
temperature (T1) to the higher temperature (T2) divided
by the temperature difference.
☻ If mass of the system is 1 g, the heat capacity is

called the specific heat of the system.
☻ For 1 mol of substance, the heat capacity is
termed as ‘molar heat capacity’
❑ The quantity (U + PV) is called the

enthalpy (H) of the system ⮚ Molar heat capacity varies with temperature
❑ Molar heat capacity at constant volume

ΔU = ΔH – PΔV
or ΔH = ΔU + PΔV @ constant volume w = 0 & ΔU = q
, 10
Heat Capacity
❑ Molar heat capacity at constant pressure (Cp)
ΔU = q - w
@ constant pressure,
there is change in As quantity (U+PV) is the ⇒
volume & some work is enthalpy (H) of the system
done
❑ Relationship between Cp & Cv ▪ For ideal gas, PV = RT (for 1 mole)
Δ(PV) = R ΔT
Heat capacity ratio,

11
Application of 1st Law to the Expansion Work
⮚ Isothermal Process (constant temperature)

▪ In an isothermal process,
the temperature stays
constant, so the pressure
and volume are
work done inversely proportional to
one another.
⇒ For an ideal gas,

The internal energy (U) ∝ Temperature (T)
if T = fixed, ΔU = 0 (according to 1st law, which deals with ΔU)
▪ If the system does work, the energy

Pressure-volume diagram
comes from heat flowing into the
system from the surrounding
# Magnitude of w depends on whether the ▪ If work is done on the system, heat
expansion is reversible or irreversible. flows out of the system to the
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surrounding.
⮚ Reversible isothermal expansion:

(as PV = nRT)
▪ Work done by the n moles of gas can be

evaluated as:
in an isothermal expansion of a perfect gas)
⮚ Irreversible Isothermal expansion ⮚ The work done by a perfect gas when it expands
reversibly and isothermally is equal to the area
under the isotherm p = nRT/V.
⮚ The work done during the irreversible
expansion against the same final pressure is
equal to the rectangular area shown slightly
darker. Note that the reversible work done is
greater than the irreversible work done.
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⮚ Adiabatic process (constant ⮚ Reversible adiabatic
▪ noheat)
heat is added/ removed from a ▪
expansion
Relation between T, V
system. and P
▪ 1st law of thermodynamics:
⇒
ΔU = w
(as no heat is allowed to enter/leave the system, q = 0)
✔ Example: A gas expanding so quickly that no heat ⇒
can be transferred. Due to the expansion work,
temperature drops. This is exactly what happens
with a carbon dioxide fire extinguisher, with the ⇒
gas coming out at high pressure and cooling as it
expands at atmos. pressure ⇒
⮚ Irreversible adiabatic
⇒ Work is done by the system at the expense of
expansion
its internal energy
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⮚ Isobaric process (constant ⮚ Isochoric process (constant
pressure) volume)
▪ the pressure is kept constant. ▪ the volume is kept constant
▪ The work done by the system in an isobaric ▪ The work done is zero in an isochoric
process is simply the pressure multiplied by the process
change in volume ✔ . Example of an isochoric system: A gas in a
✔ Example of an isobaric system: A gas, being box with fixed walls
slowly heated or cooled, confined by a piston in a
cylinder.
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2nd Law of Thermodynamics
▪ Why we need for the 2nd law of thermodynamics? ⮚ The 1st law uses the internal energy to
→ The 1st law of thermodynamics does not tell us identify permissible changes
anything about the direction of change. The⮚ The 2nd law uses the entropy to identify
direction of spontaneous change of a process is which of these permissible changes are
defined by the 2nd law of thermodynamics spontaneous.
❑ 2nd law of thermodynamics → A spontaneous process points towards
the direction in which the total entropy
▪ Heat does not flow spontaneously from a cool
increases.
body to a hotter body.
⮚ Entropy (S) is a state function.
▪ The entropy (S) of an isolated system
increases in the course of a spontaneous ⮚ Thermodynamic definition of entropy
change. ΔS > 0 → The thermodynamic definition of entropy
tot
Where, Stot = S + Ssur concentrates on the change in entropy

S = the entropy of the system of interest, & (dS) that occurs as the result of a
Ssur = the entropy of the surroundings physical or chemical process.
→ dqrev is the energy transferred as heat
# Note: when considering applications of the 2 law – it
nd
reversibly to the system at the absolute
is a statement about the total entropy of the overall temperature T.
isolated system (the ‘universe’), not just about the
entropy of the system of interest. 16
Entropy
▪ Process that leads to an increase in entropy (ΔS > 0)
⮚ Entropy change for the system of an
isothermal expansion of a perfect gas
☻ Notice the increasing disorder in above processes 17

Entropy
⮚ Total Entropy change in irreversible ⮚ Isothermal Reversible expansion
(spontaneous) process of a perfect gas
✔ example: Isothermal expansion of an ideal gas
at constant temperature into vacuum
⮚ Clausius inequality
⇒ All spontaneous process occurring in

Nature are irreversible and entropy of the
universe is increasing continuously. 18
Entropy
▪ The 1st law & the 2nd law of thermodynamics were summed up by German Physicist Rudolf Clausius as below:
The energy of the universe remains constant; the entropy of the universe tends towards a maximum
⮚ Entropy change during different processes ⮚ Heat engine
▪ Its a device which transforms heat into work
▪ This happens in a cyclic process
▪ Heat engines require a hot reservoir to supply energy
(QH) and a cold reservoir to take in the excess energy (QC)
– QH is defined as positive, QC is defined as negative
⮚ Carnot Cycle
▪ A Carnot cycle (named after the French engineer Sadi

Carnot) consists of four reversible stages in which a gas
(the working substance) is either expanded/compressed in
various ways
▪ To demonstrate the maximum convertibility of heat into
work
▪ The system consists of 1 mole of an ideal gas which is
subjected to four strokes
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⮚ Four stages of Carnot Cycle:
A. 1st stroke: B. 2nd stroke:
Curve AB: A🡪 B: Isothermal expansion at Th Curve BC (B → C): Adiabatic expansion,
Work done by the gas Work done by the gas
C. 3rd stroke:
Curve CD (C → D): Isothermal compression at TC,
Work done on the gas.
D. 4th stroke:
Curve DA (D → A): Adiabatic compression
Work done on the gas
⮚ Another statement of the 2nd Law:

– It is impossible for any process to have as its sole result
the transfer of heat from a cooler object to a warmer
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object
Carnot Cycle
⮚ Four stages of Carnot Cycle: A. 1st stroke:

Curve AB: A🡪 B: Isothermal expansion at Th
Work done by the gas
⇒ The gas is placed in thermal contact with QH (at Th) and
undergoes reversible isothermal expansion from A to B.
⇒ The entropy change is qh/Th ( qh = the energy supplied to
the system as heat from the hot source)
B. 2nd stroke:
Curve BC (B → C): Adiabatic expansion,
Work done by the gas
⇒ Contact with QH is broken & the gas undergoes
reversible adiabatic expansion from B to C.
⇒ No energy leaves the system as heat, ΔS = 0
⇒ The expansion is carried on until the temperature of
the gas falls from Th to Tc (the temperature of Qc)
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Carnot Cycle
C. 3rd stroke:
Curve CD (C → D): Isothermal compression at TC,
Work done on the gas.
▪ The gas is placed in contact with the cold sink (Qc) and
undergoes a reversible isothermal compression from C to D at
Tc.
▪ Energy is released as heat to the cold sink; the entropy change of
the system = qc/Tc, where qc is negative.
D. 4th stroke:
Curve DA (D → A): Adiabatic compression
Work done on the gas
▪ Contact with Qc is broken and the gas undergoes
reversible adiabatic compression from D to A such
that the final temperature is Th.
▪ No energy enters the system as heat, so the change
in entropy is zero.
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Carnot Cycle
▪ The area enclosed by the four curves represents the net

work done by the engine in one cycle
▪ The total change in entropy around the cycle is the sum
of the changes in each of these four steps:
Efficiency of a heat engine

• The thermal efficiency of a heat engine is
• Another statement of the 2nd Law:

– It is impossible for any process to have as its sole
result the transfer of heat from a cooler object to
[Kelvin’s statement] a warmer object [Clausius’s statement] 23
Application of the Carnot Cycle
∙ Energy efficiency of the

Carnot cycle is independent
of its working substance.
∙ Any cyclic process that
absorbs heat at one
temperature and rejects
heat at another
temperature and is
reversible has the energy
efficiency of a Carnot cycle.
→ Thermal devices or thermal machines are one of

the applications of this cycle.
→ Refrigeration, Air conditioners & Heat pumps
✔ The heat pumps to produce heating,
● These appliances are heat engines operating
✔ the refrigerators to produce cooling,
in reverse.
✔ the steam turbines used in the ships,
● By doing work, heat is extracted from the cold
✔ the combustion engines of the combustion vehicles
reservoir & exhausted to the hot reservoir
✔ the reaction turbines of the aircraft 24
Temperature & Free Energy
⮚ Thermodynamic Temperature ⮚ Free energy and the spontaneity

▪ Suppose an engine works reversibly
between a hot source at a temperature
Th and a cold sink at a temperature Tc,
then it follows that ▪ It is not always easy to know the entropy change of
both system and the surrounding
Tc = (1 − η)Th
▪ We can express this in terms of G (the free energy
▪ Kelvin used this expression to define the function) and thus can device a criterion of spontaneity
thermodynamic temperature scale in in terms of the state function of the system.
terms of the efficiency of a heat engine in ▪ There are few assumptions:
which the hot source is at a known → Assumption no 1:
temperature and the cold sink is the object The system is in thermal equilibrium with its surroundings at
of interest. a temperature T.
▪ The Kelvin scale (which is a special case of → Assumption no 2:
the thermodynamic temperature scale) is Heat transfer between the system and the surrounding
currently defined by using water at its happens at constant volume
triple point as the notional hot source and → Assumption no 3:
defining that temperature as 273.16 K Heat transfer between the system and the surrounding
exactly. happens at constant pressure. 25
Free Energy
⮚ Under the Assumption 1 & Assumption 2 ▪ The criterion of spontaneity in terms of Gibbs Free
energy change (dG) and Helmholtz energy (dA)
⮚ In an endothermic reaction:
dH > 0
⇒ TdS ≥ dU but if such a reaction is to be spontaneous at constant
dA=dU−TdS [A = Helmholtz free energy] temperature and pressure, G must decrease.
⇒ A=U−TS ▪ as dG = dH − TdS
it is possible for dG to be
negative provided that
⮚ Under the Assumption 1 & Assumption 3 the entropy of the
system increases so
much that TdS outweighs
⇒ TdS ≥ dH dH.
⇒ Endothermic
dG=dH−TdS [G = Gibbs free energy] reactions are
⇒ G=H−TS therefore driven by
the increase of
entropy of the system 26
Free Energy
⮚ In an exothermic
reactions ⮚ At chemical
▪ commonly spontaneous
because dH < 0 & then dG < 0 provided TdS is not equilibrium,
so negative that it outweighs the decrease in ⮚ dG = 0
enthalpy. ▪ Free energy change with
temperature and pressure:
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Spontaneity of a Chemical Reaction
• A spontaneous reaction is a reaction that favors the formation of products at the conditions
under which the reaction is occurring. Spontaneous processes may be fast or slow, but they occur
without outside intervention.
Ex. i) Conversion of graphite to diamond is slow;
ii) A burning fire is relatively a fast reaction.
• "In any spontaneous process there is always an increase in the entropy of the universe“
• For a given change to be spontaneous, ΔSuniverse must be positive.
Gibbs Free Energy

• Free energy is energy that is available to do work. The free energy change of a reaction is a
mathematical combination of the enthalpy change and the entropy change.
• The change in enthalpy, change in entropy and change in free energy of a reaction are the
driving forces behind all chemical reactions.
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Conditions for Spontaneity of a Chemical Reaction
(Changes in Enthalpy (ΔH), Entropy (ΔS), and Free Energy (ΔG))
• A spontaneous reaction is one that releases free energy, and so the sign of ΔG must be negative.
Since both ΔH and ΔS can be either positive or negative, depending on the characteristics of the
particular reaction, there are four different possible combinations as shown in the table below.
ΔH◦ ΔS◦ ΔG◦

Negative Positive Always negative
Negative at higher temperatures, positive at lower

Positive Positive
temperatures
Negative at lower temperatures, positive at higher

Negative Negative
temperatures
Positive Negative Always positive

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3rd Law of Thermodynamics
▪ At T = 0, all energy of thermal motion has
been quenched and in a perfect crystal all
the atoms/ions are in a regular, uniform
array.
▪ The localization of matter and the absence
of thermal motion suggest that such
materials also have zero entropy.
▪ Statistical or microscopic definition of entropy:
S = k ln W
→ When T = 0, W = 1
where, S = the entropy, ∴ S = k lnW
k = Boltzmann constant, =0
W = the number of microstates ⇒ if the value zero is ascribed to the entropies of elements
or the total number of ways a in their perfect crystalline form at T = 0, then all perfect
molecular state can be crystalline compounds also have zero entropy at T = 0
distributed over the energy
states for a specific value of total
energy. ⮚ Third law of thermodynamics:
The entropy of all perfect crystalline substances is zero at T = 0. 30
Part-B
Chemical Kinetics
- Concept of activation energy and energy barrier
- Arrhenius equation
- effect of catalysts (homo and heterogeneous)
- Enzyme catalysis (Michaelis-Menten Mechanism).
31
• The chemistry that deals with the reaction rates is known as chemical
kinetics.
• It plays an important role in the production of chemicals on an industrial scale
and the decay of radioactive isotopes used in medicine.
• Chemical kinetics is also useful in providing information about how reactions
occur—the order in which chemical bonds are broken and formed during the
course of a reaction.
• Experimental information on the rate of a given reaction provides important
evidence that helps us formulate a reaction mechanism, which is a step-by-
step, molecular-level view of the pathway from reactants to products.
It is to be contrasted with thermodynamics, which deals with the direction in
which a process occurs but in itself tells nothing about its rate
Factors That Affect Reaction Rates
1. Physical state of the reactants- homogeneous, involving either all gases or all
liquids, or as heterogeneous, in which reactants are in different phases.
2. Reactant concentrations.
3. Reaction temperature.
4. The presence of a catalyst.
Reaction Rates
On a molecular level, reaction rates depend on the frequency
of collisions between molecules. The greater the frequency of
collisions, the higher the reaction rate.
⮚ The change in concentration of reactants or products per
unit time.
⮚ Here, the instantaneous rate of disappearance of one of
the reactants (A or B) at a given time, t (at constant
volume) is −d[R]/dt.
⮚ Similarly, the rate of formation of one of the products is
d[P]/dt. (Note the change in the sign)
⮚ The negative sign indicates that the concentration is
decreasing with time.
Concentration and the rates of reactions
Consider a general reaction, A + B → C
• The rate of this reaction can be expressed either as the rate of disappearance of reactant
‘A’ and ‘B’ or as the rate of appearance of product ‘C’.
• The rate of reaction will be:
• Average rate of appearance /disappearance of A, B or C = change in concentration of
A, B or C
change in time
Now, consider another general reaction: aA + bB → cC + dD

where a, b, c & d are stoichiometric coefficients
The rate of reaction will be:
The rates of reactions
Sample Questions:
Write rate expressions for the following reactions:
1. NO2 (g) + CO (g) → NO (g) + CO2 (g)
2. 2HI (g) → H2 (g) + I2 (g)
Solution:
1.
2.
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Rate laws and rate constants
⮚The rate law is the relationship between the rate and the concentration, which
are related by a proportionality constant ‘k’, known as rate constant.
For the general reaction:
aA + bB → cC + dD
the rate law generally has the form
rate = k [A]m[B]n
where exponents ‘m’ and ‘n’ are order of reaction in ‘A’ and ‘B’, respectively and
‘k’ is the rate constant.
This above equation is called the rate law of the reaction.
Exponents m and n are typically small whole numbers, whose values are not necessarily
equal to the coefficients a and b from the balanced equation.
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Rate laws and rate constants…
Important points about rate laws and rate constant:
⮚ Rate law is a result of experimental observation. You CANNOT look

at the stoichiometry of the reaction and predict the rate law (unless
the reaction is an elementary reaction).
⮚ The rate law is not limited to reactants. It can have a product term,
For example: rate = k[A]m[B]n[C]c
⮚ The rate constant is independent of the concentrations but depends

on the temperature.
⮚ The units for k vary. Determine units for k by considering units for
rate and for concentration.
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Order of a reaction
• It is the sum of the exponents of the concentrations in the rate law equation
• It can be integers, fractions, negative or positive.
• It can be determined only experimentally
• It may not be equal to the number of molecules of reactants
Ex. For the reaction: A+B→C
rate = k [A]m [B]n
• where, m is the order of reaction with respect to A, n is the order of reaction with respect to
B.
• The overall reaction order is the sum of the exponents in the rate law = m + n
❖ m = 0 (Zero order k [A]0)
❖ m = 1 (First order k [A]1)
❖ m = 2 (Second order k [A]2)
Examples:
H2 + Cl2 → 2HCl. Rate = k [H2]0 [Cl2]0 (Zero order)
SO2Cl2(g) → SO2(g) + Cl2(g) Rate = k [SO2Cl2]1 (First order)
2NO2 → 2 NO + O2 Rate = k [NO2]2 (Second order)
2NO(g) + 2H2(g) → 2N2 (g) + 2H2O (g) Rate = k [NO]2 [H2]1 (Third order)
CH3COOC2H5 + H2O → CH3COOH + C2H5OH Rate = k [CH3COOC2H5]1[H2O]0 (pseudo-first-order)
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Molecularity of a reaction
• It is the number of molecules or ions that participate in the rate determining step
• It is a theoretical concept and it can be determined from rate determining step
(slowest step).
• It is always an integer between 1 to 3, as it is not possible to colliding of four or
more molecules simultaneously.
• For elementary reactions (single step reactions):
– It is the sum of stoichiometry coefficients of the reactants
Ex. H2 + I2 → 2HI
Molecularity = 1 + 1 = 2
• For complex reactions:
– The sum of the number of reactant in the rate determining steps gives the
molecularity
First-Order Reactions
A first-order reaction is one whose rate depends on the concentration of a single reactant raised to
the first power.
If a reaction of the type A → products is first order, the rate law is:
Rate = Straight line equation (y = mx + c)
Separate concentration and time terms
y = mx + c
Integrating over the limits [A]0 to [A]t and 0 to
If we plot ln [A]t versus time, then we ln[A]0
t, will get a straight line having negative
slope (-k).
Rate constants can be determined

from experiment by plotting data in this
manner. -k
Half-Life of First Order Reaction
The half-life of a reaction (t1/2)
• It is the time required for the concentration of a reactant to reach half its initial value, [A]t1/2 = ½
[A]0.
• Half-life is a convenient way to describe how fast a reaction occurs, especially if it is a first-order
process.
• A fast reaction has a short half-life.
• We can determine the half-life of a first-order reaction by substituting
[A]t1/2 = ½ [A]0 for [A]t and t1/2 for t in Equation :
ln ½ [A]0 = -k t1/2
[A] 0
ln ½ = -k t1/2
t1/2 = - ln ½ = 0.693
k k
Ex. The conversion of
methyl isonitrile (CH3NC) to its isomer acetonitrile (CH3CN) at
199 °C.
ln[CH3NC]t = -kt + ln[CH3NC]0
Figure (a) shows how the pressure of this gas varies with time.
Figure (b) shows that a plot of the natural logarithm of the pressure versus time is a straight line.
The slope of this line is -5.1 X 10-5 s-1.∴k = 5.1 X 10-5 s-1
Second-Order Reactions
A second-order reaction is one for which the rate depends either on a reactant concentration raised
to the second power or on the concentrations of two reactants each raised to the first power.
For Ex: in reactions A → products or A + B → products that are second order with respect to only
one reactant, A:
Rate =
• This equation, has four variables, k, t, [A]0, and [A]t,
and any one of these can be calculated knowing the
other three.
• This Equation also has the form of a straight line (y =
With the use of calculus, this differential rate mx + c).
law can be used to derive the integrated rate • If the reaction is second order, a plot of ‘1/ [A]t’
law for second-order reactions: versus ‘t’ yields a straight line with slope k and y-
intercept 1/ [A]0.
• One way to distinguish between first and second-
order rate laws is to graph both ln[A]t and 1/ [A]t
against t.
• If the ln[A]t plot is linear, the reaction is first order;
• if the 1/ [A]t plot is linear, the reaction is second order.
Half-Life of Second-Order Reactions
The half-life of a chemical reaction is the time taken for half of the initial amount of reactant to
undergo the reaction.
Therefore, while attempting to calculate the half life of a reaction, the following substitutions must
be made:
Zero-Order Reactions
• We have seen that in a first-order reaction the concentration of a reactant ‘A’ decreases
nonlinearly, as shown by the red curve in Figure.
• As [A] declines, the rate at which it disappears declines in
proportion.
• A zero-order reaction is one in which the rate of
disappearance of A is independent of [A].
• The rate law for a zero-order reaction is
Rate =
The integrated rate law for a zero-order reaction is Figure. Comparison of first-order and zeroorder
reactions for the disappearance of reactant A with time
where [A]t is the concentration of A at time t and [A]0 Ex. The most common type of zero-order reaction occurs
when a gas undergoes decomposition on the surface of
is the initial concentration.
a solid.
This is the equation for a straight line with vertical 2N2O Pt(hot) 2N2+O2
intercept [A]0 and slope -kt, as shown in the blue Photochemical reaction:
curve in Figure. H2 (g) + Cl2 (g) hv 2HCl(g)
Half-Life of a Zero Order Reaction
The timescale in which there is a 50% reduction in the initial population is referred to as half-
life. Half-life is denoted by the symbol ‘t1/2’.
Pseudo First Order Reaction
A pseudo first-order reaction can be defined as a second-order or bimolecular reaction
that is made to behave like a first-order reaction.
⮚ This reaction occurs when one reacting material is present in great excess or is maintained at
a constant concentration compared with the other substance.
A+B→C
So, if component B is in large excess and the concentration of B is very high as compared to that
of A, the reaction is considered to be a pseudo-first-order reaction with respect to A.
If component A is in large excess and the concentration of A is very high as compared to that of B,
the reaction is considered to be pseudo-first order with respect to B.
For example:
CH3COOC2H5 + H2O → CH3COOH + C2H5OH
Rate = k [CH3COOC2H5]
**The concentration of water is very high and thus does not change much during the course
of the reaction.
47
Temperature and Rate
• The rates of most chemical reactions increase as the
temperature rises.
• The faster rate at higher temperature is due to an increase
in the rate constant with increasing temperature.
• For example, CH3NC → CH3CN
The rate constant and, hence, the rate of the reaction increase
rapidly with temperature, approximately doubling for each 10
°C rise. Temperature dependence of the rate constant
for methyl isonitrile conversion to acetonitrile
The Collision Model
• The greater the number of collisions per second, the greater the reaction rate.
• As reactant concentration increases, therefore, the number of collisions increases, leading
to an increase in reaction rate.
• According to the kinetic-molecular theory of gases, increasing the temperature increases
molecular speeds. As molecules move faster, they collide more forcefully (with more
energy) and more frequently, both of which increase the reaction rate.
The Orientation Factor:
• In most reactions, collisions between molecules result in a chemical reaction only if the
molecules are oriented in a certain way when they collide.
• The relative orientations of the molecules during collision determine whether the atoms are
suitably positioned to form new bonds.
For example,
Cl + NOCl → NO + Cl2
• Molecular collisions may or may not lead to a chemical reaction between Cl and NOCl.
Activation Energy:
• In 1888 the Swedish chemist Svante Arrhenius suggested that molecules must possess a
certain minimum amount of energy to react.
• According to the collision model, this energy comes from the kinetic energies of the colliding
molecules.
• Upon collision, the kinetic energy of the molecules can be used to stretch, bend, and ultimately
break bonds, leading to chemical reactions.
• The minimum energy required to initiate a chemical reaction is called the activation
energy, Ea, and its value varies from reaction to reaction.
Energy is needed to overcome a barrier between initial and final states.

For example, • The difference between the energy of the starting molecule and the highest energy
along the reaction pathway is the activation energy, Ea.
• The molecule having the arrangement of atoms shown at the top of the barrier is
called either the activated complex or the transition state.
• The rate constant depends on the magnitude of Ea
• Generally, the lower the value of Ea is, the larger the rate constant and the faster the
reaction.
Energy profile for conversion of methyl isonitrile
(H3CNC) to its isomer acetonitrile (H3CCN).
The effect of temperature on the distribution of kinetic energies of
molecules in a sample.
• Figure shows the distribution of kinetic energies for two temperatures, comparing
them with the minimum energy needed for reaction, Ea.
• At the higher temperature a much greater fraction of the molecules have kinetic
energy greater than Ea, which leads to a greater rate of reaction.
Arrhenius equation
where, k is rate constant, Ea is the activation

Arrhenius equation (non exponential form)
energy,
A is the pre-exponential (frequecy) factor is
constant, and RT is the average kinetic energy i.e.,
R is the gas constant (8.314 J/mol-K), and T is the
absolute temperature. • value of from intercept at infinite T
❖ A graph of lnk versus 1/T is a straight line (i.e.; 1/T=0)
when the reaction follows the behavior • value of Ea from the slope.
described by the Arrhenius equation.

❖ The higher the activation energy, the
stronger the temperature dependence of the
rate constant (i.e., the steeper the slope).
❖ If a reaction has zero activation energy, its
rate is independent of temperature.
53
Consider a series of reactions having these energy profiles:
Rank the forward rate constants from smallest to largest assuming all three reactions have
nearly the same value for the frequency factor A.
SOLUTION
• The lower the activation energy, the larger the rate constant and the faster the reaction.
• The value of ΔE does not affect the value of the rate constant.
• Hence, the order of the rate constants is 2 < 3 < 1.
Catalysis
• A catalyst is a substance that changes the speed of a chemical reaction without undergoing a
permanent chemical change itself.
• Most reactions in the body, the atmosphere, and the oceans occur with the help of catalysts.
• Much industrial chemical research is devoted to the search for more effective catalysts for
reactions of commercial importance.
• The phenomenon of alteration of the rate of a reaction by a catalyst is known catalysis.
• The science and technology of catalysis is of great significance as it affects our daily life.
• The catalytic processes contribute greater than 30-40% of global GDP
• Four major sectors of the world economy involve catalytic processes.
✔ Petroleum and Energy Production,
✔ Chemicals and Polymer Production,
✔ Food industry and
✔ Pollution control.
Catalytic reactions Types of catalysis
• Catalysts work by providing alternative mechanism involving a
different transition state of lower energy.
• Thereby, the activation energy* of the catalytic reaction is lowered
compared to the uncatalyzed reaction . Following are the main types of catalysis:
1. Homogeneous catalysis
2. Heterogeneous catalysis
3. Enzyme catalysis
Figure: Schematic diagram to illustrate the

effect of catalyst on activation energy of
reactions.
1. Homogeneous catalysis
In a reaction, if the catalyst is present in the same phase as the
reactants, it is called a homogeneous catalyst and the phenomenon is
homogeneous catalysis. Such catalysis can take place in gaseous
reaction or reactions in solution.
Figure: Schematic diagram to illustrate the homogeneous catalysis.
These chemicals help in attaining the equilibrium more quickly by

increasing the rates of both the forward and reverse reactions to an
extent. 57
Examples of homogeneous catalysis in the gas phase
(1) Oxidation of sulphur dioxide, SO2, by oxygen to sulphur trioxide, SO3, in
presence of nitric oxide, NO, in the Chamber Process for sulphuric acid manufacture.
2SO2 (g) + O2 (g) → 2SO3 (g)
here, NO acts as a catalyst.
(2) The following reaction in the gas phase is catalyzed by traces of chlorine gas,
particularly in presence of light.
2N2O (g) → 2N2 (g) + O2 (g)
In presence of light chlorine forms chlorine radicals, which react with N2O forming
the intermediate radical ClO*.
The proposed mechanism is:
Step 1: N2O (g) + Cl* (g) → N2 (g) + ClO*(g)
Step 2: 2ClO*(g) → Cl2 (g) + O2 (g)
58
Examples of homogeneous catalysis in the solution phase
(3) Hydrolysis of ester in the presence of acid and alkali:

CH3COOC2H5 (l) + H2O (l) → CH3COOH (aq) + C2H5OH (aq)
(4) Hydrolysis of sucrose (cane sugar) into glucose and fructose in

presence of minerals acids acting as catalysts:
C12H22O11 (aq) + H2O (l) → C6H12O6 (aq) +
C6H12O6 (aq) (glucose) (fructose)
(cane sugar)
59
The decomposition of aqueous hydrogen peroxide, H2O2(aq) , into water and
oxygen:
2 H2O2(aq) → H2O(l) + O2 (g) ↑
In presence of catalyst:
2Br − (aq) + H2O2(aq) + 2H+ (aq) → Br2 (aq) + 2H2O(l)
Br2 (aq) + H2O2(aq) → 2Br − (aq) + 2H+ (aq) + O2 (g) ↑
60
2. Heterogeneous catalysis
If the catalyst is present in a different phase than the reactants is called
heterogeneous catalyst and the phenomenon is known heterogeneous
catalysis.
In heterogeneous catalysis the reactions take place at the interface of two

phases. The catalyst is, often a solid and adsorbs a liquid or a gas. This type
of catalysis is of great importance in many industrial processes.
Figure: Schematic diagram to illustrate the heterogeneous catalysis.
61
Examples of Heterogeneous catalyst
(a) Manufacture of ammonia by the Haber process. Iron (Fe) acts as catalyst.
N2 (g) + 3H3 (g) → 2NH3 (g)
(b) Manufacture of sulphuric acid by the Contact process. Vanadium pentoxide (V2O5)
or platinum are catalysts for the production of SO3 (g) from SO2 (g) and O2 (g).
2SO2 (g) + O2 (g) → 2SO3 (g)
(c) Catalysts used in many reactions in the petroleum and polymer industries. There
are cases of heterogeneous catalysis where a reaction in the liquid phase is
catalysed by a substance in the solid state. An example is the decomposition of
H2O2 (aqueous) by MnO2 (s).
2H2O2 (aq) → 2 H2O (l) + O2 (g)
(d) Examples of reactions in which both the reactant and the catalyst are in the
solid phase. The decomposition of KClO3 is catalysed by solid MnO2.
2 KClO3 (s) → 2KCl (s) + 3O2 (g)
62
Enzyme catalysis
• Biological catalysts known as enzymes are necessary for many of the chemical reactions occur
in an extremely complex system of the human body.
• Enzymes are protein-based molecules that can
process certain chemical reactions
• These reactions occur at a localized site, called
the active site, at the rate much faster than a
normal chemical reaction.
• Substrate is the molecule that fits into the active
site of the enzyme and undergoes transformation
to a product.
• Example of an enzyme catalysed reaction is catalase that converts
hydrogen peroxide to water and oxygen.
• It is an important enzyme protecting the cell from oxidative damage by
reactive oxygen species (ROS)
Reaction catalysed by the

enzyme, catalase H2O2 → H2O + O2
Enzymes speed up reactions.
Mechanism of enzyme-catalyzed reactions
❑ Enzyme-catalyzed reactions work in a lock
and key fashion.
❑ The substrate uniquely fits like a key into
the active site of the enzyme, forming a
lock-key complex.
❑ The substrate is converted into the product
by the enzyme at the active site.
❑ The product is then released from the active
Enzymes’ effect on the activation energy site.
❑ Enzymes lower the activation energy for reactions. The
lower the activation energy, the faster the rate of the
reactions.
❑ For example: the enzyme catalase reduces the
activation energy for the decomposition of hydrogen
peroxide to 8 kJ mol-1, corresponding to an acceleration
of the reaction by a factor of 1015 at 298 K.
❑ A generic
E +equation
S for
ES the complex
P + E formation is as
follows:
Michaelis-Menten equation
E+S ES P+E
❑ Michaelis-Menten equation is a commonly used model that assumes that the concentration
of the enzyme remains constant.
❑ The enzyme reacts with the substrate for form an enzyme-substrate complex, which leads to
the synthesis of the product and the release of the enzyme
ka kb
E +S ES P+E
ka ’
❑ Where, ka is the rate of formation of ES, ka’ is the rate of dissociation of ES, and kb is the
rate of formation of P from ES.
65
Michaelis-Menten Mechanism
One of the earliest descriptions of the action of enzymes is the Michaelis-Menten mechanism.
The proposed mechanism, with all species in an aqueous environment, is as follows.
Step 1: The bimolecular formation of a combination, ES, of the enzyme E and the substrate S:
E + S → ES Rate of formation of ES = ka[E][S]
Step 2: Unimolecular decomposition of the complex:

Rate of decomposition of ES = ka’ [ES]
ES → E + S
Step 3: The unimolecular formation of products P and the release of the enzyme from its combination
with the substrate:
ES → P + E Rate of formation of S = kb [ES]
66
Module-2:
Metal Complexes and
Organometallics
1
Contents…..(6 hours)
Inorganic complexes - structure, bonding and application;
Organometallics – introduction, stability, structure and applications

of metal carbonyls, ferrocene and Grignard reagent;
Metals in biology: haemoglobin and chlorophyll- structure and

property).
2
Inorganic Complexes: Structure, Bonding and Applications
❖ Double Salt: Double Salts and Coordination Compounds
Ferric alum
(NH4)2SO4.Fe2(SO)4.24H2O
In water: NH4+, SO42-, Fe3+
❖Co-ordination Compounds
3Cl– Fe(CN)2 + 4KCN Fe(CN)2.4KCN

(counterion)
4K+ + [Fe(CN)6]4-
ligand
(coordination sphere) M
N forms a coordinate covalent bond

to the metal
Ligands
▪ Molecule or ion having a lone electron pair that can be used to form a bond to a
metal ion (Lewis base).
▪ coordinate covalent bond: metal-ligand bond
▪ monodentate : one bond to metal ion
▪ bidentate : two bonds to metal ion
▪ polydentate : more than two bonds to a metal ion possible
4
Chelating Agents
• Bind to metal ions removing them
• Important biomolecules like heme
from solution.
and chlorophyll are porphyrins
• Phosphates are used to tie up
Ca2+ and Mg2+ in hard water to
prevent them from interfering with
detergents.
Werner Coordination Theory
Werner's Theory: Alfred Werner, Swiss chemist put forward a theory to explain the
formation of complex compounds.
Limitations:
1. Bonding within coordination sphere.
2. Square planar (or) Tetrahedral
Lewis Acid Base Theory - Gilbert N. Lewis, 1920s
❖ Lewis Acid/Base reactions: Base: electron pair donor; Acid: electron pair
acceptor
❖ Ligands: Lewis bases ; Metals: Lewis acids ; Coordinate covalent bonds
❖ Metal Complexes - Formation of a complex was described as an acid - base
reaction according to Lewis
Sidgwick’s Rule
❖ Sidgwick’s Effective atomic number (EAN) rule is based on the octet

theory of Lewis and this is the first attempt to account for the bonding in
complexes.
Valence Bond Theory (Linus Pauling, 1931)
Valence bond theory predicts that the bonding in a metal complex arises from
overlap of filled ligand orbitals and vacant metal orbitals.
8
Tetrahedral Geometry
• Tetrahedral copper complex [CuCl4]2-
3d 4s 4p
Cu ground
state 3d94s2
Cu2+
4 e– pairs by Cl– ions
• One unpaired electron - paramagnetic and attracted by magnets

Square Planar Geometry
• Square planar nickel complex
[Ni(CN)4]2-
3d 4s 4p
Ni
(3d84s2)
Ni2+
[Ni(CN)4]2-
dsp2
• All paired electrons – diamagnetic - weakly repelled by magnets
Octahedral sp3d2 Geometry
Gives [CoF6]3– four unpaired electrons, which makes it paramagnetic and is called a high-spin
complex.
Ground state Co= (3d74s2)
Octahedral d2sp3 Geometry
[Fe(CN)6]3- Fe: (3d64s2)
3d 4s 4p
Fe+3
[Fe(CN)6]3-
CN– Strong ligand d2sp3

Bonding in Coordination Compounds
❖ Many of the properties of metal complexes are dictated by their electronic structures.
Crystal field theory (CFT)
❖ Electronic structure can be explained by an ionic model that attributes formal charges on to the metals
and ligands. This forms basis of crystal field theory (CFT), which is considered as the core concept in
inorganic chemistry.
❖ Consider bonding in a complex to be an electrostatic attraction between a positively charged nucleus
and the electrons of the ligands.
▪ Electrons on metal atom repel electrons on ligands.
▪ Focus particularly on the d-electrons on the metal ion.
❖ Ligand field theory (LFT) and the molecular orbital theory (MO) are considered sophisticated models as
compared to CFT. LFT explains complexes, wherein, the interactions are covalent.
Orbital occupancy for high- and low-spin complexes of d4 through d7 metal ions
high low spin:

high low spin: spin: strong-
spin: strong- weak- field ligand
weak- field ligand field
field ligand
ligand
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
[Co(NH3)6]3+ > [Co(NH3)6]2+
[Co(NH3)6]3+ = 23,000 cm-1 (3d)
[Rh(NH3)6]3+ = 34,000 cm-1 (4d)
[Ir(NH3)6]3+ = 41,000 cm-1 (5d)

Spectrochemical Series
▪ For a given ligand, the color depends on the oxidation
state of the metal ion.
I- < Cl- < F- < OH- < H2O < SCN- < NH3 < en < NO2- < CN- < CO
WEAKER FIELD STRONGER FIELD

❖ Complexes of cobalt (III)
show the shift in color due
SMALLER Δ LARGER Δ
to the ligand.
❖ (a) CN–, (b) NO2–, (c) phen,
LONGER λ SHORTER λ (d) en, (e) NH3, (f) gly, (g)
H2O, (h) ox2–, (i) CO3 2–
• For a given metal ion, the color depends on the ligand.
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
Spectrochemical series (strength of ligand interaction)
Effect of ligand on splitting energy
Increasing Δ
Cl- < F- < H2O < NH3 < en < NO2- < CN-
Increasing Δ
Low spin – color variations shown with increasing CFSE (Cr3+ = 24-3-18 = d3)
Applications of Coordination Compounds
❖Coordination compounds are of great importance.

❖Play many important functions in the area of analytical chemistry,
metallurgy, biological systems, industry and medicine.
• Catalysis
• Extraction of metal ions
• Analytical chemistry (development of numerous analytical
methods)
• Hardness estimation -
• Biological importance
• Medicinal application
• Industrial application
Extraction / Purification of metal
⮚ Extraction
❖ processes of metals, like those of silver and gold, make use of complex formation.
❖ These noble metals are extracted from their ore by the formation of cyanide complexes -
dicyanoargentite(I) - [Ag(CN)2]– and dicyanoaurate (I) - [Au(CN)2]– in the presence of oxygen
and water, from which the metallic forms can be separated by the addition of zinc.
▪ Ag2S + 4NaCN 🡪 2 Na[Ag(CN)2] + Na2S
▪ 2 Na[Ag(CN)2] + Zn 🡪 Na2[Zn(CN)4] + 2Ag↓
❖ Purification of metals can be achieved through formation and subsequent decomposition of

their coordination compounds. For example, impure nickel is converted to [Ni(CO)4], which is
decomposed to yield pure nickel.
Analytical chemistry
❖ In the qualitative methods of analysis, complex formation is of immense importance in the
identification and separation of most inorganic ions.
❖ Familiar colour reactions given by metal ions with a number of ligands (especially chelating
ligands), as a result of formation of coordination entities, form the basis for their detection and
estimation by classical and instrumental methods of analysis.
Examples of such reagents include EDTA, DMG (dimethylglyoxime), α–nitroso, β–
naphthol, cupron, etc.
❖ Cu is more stable than Cd. Therefore, on passing H2S only CdS is precipitated. Thus Cd2+ ion
easily detected in the presence of Cu2+ ions.
• Cu2+ + 4CN- 🡪 [Cu(CN)4]2-
• Cd2+ + 4CN- 🡪 [Cd(CN)4]2-
❖ Presence of Co and Fe can be detected by the formation of blue and blood red color
thiocyanate complexes respectively
20
Detection of Complex formation
❖ Formation of Precipitate
Ni2+ + 2 HDMG [Ni(DMG)2] + 2H+
❖ Ni2+ and Pd2+ form insoluble colored precipitates with dimethyglyoxime

Biological Importance
❖ Pigment responsible for photosynthesis,
chlorophyll, is a coordination compound of
magnesium.
❖ Haemoglobin, the red pigment of blood
which acts as oxygen carrier is a
coordination compound of iron.
❖ Vitamin B12, cyanocobalamine, the anti-
pernicious anaemia factor, is a coordination
compound of cobalt.
❖ Other compounds of biological importance
with coordinated metal ions are the
enzymes like, carboxypeptidase A and
carbonic anhydrase (catalysts of biological Heme B: Heme B is a porphyrin (four linked pyrrole rings)
systems) that readily binds iron, as shown. This is an example of a
❖ Metalloprotein with the metal ion cofactor biomolecule that contains non-protein ligands for a
transition metal.
have many diverse functions including
transport, storage, and signal transduction.
Medicinal Application
❖ To treat problems caused by the presence of
metals in toxic proportions in plant/animal systems,
chelate therapy is used.
• Excess of copper and iron are removed by the
chelating ligands D–penicillamine and
desferrioxime B via the formation of coordination
compounds.
❖ EDTA is used in the treatment of lead poisoning.
❖ Coordination compound of platinum effectively

inhibit the growth of tumours. cisplatin - cis
[PtCl2(NH3)2], and related compounds.
Chelation therapy
❖ D-penicillamine - Used in the treatment for
poisoning by heavy metals, including Wilson's
disease (build-up of copper in the body).
❖ Naturally occurring compounds such as
desferrioxamine B, belong to a group of
compounds called siderophores and are used
by bacteria to assist in the uptake of iron, can
also be used to remove unwanted iron by
chelation therapy.
▪ First World War - poisonous gases used in

the war was b-chlorovinyldichloroarsine
(Lewisite).
▪ Reacts with the SH groups of various
important enzymes British Anti-Lewisite
(BAL), 2,3-dimercaptopropanol. forms
stronger complex with arsenic – acts as an
antidote.
Industrial applications
• Coordination compounds are used as catalysts for many industrial
processes. Examples rhodium complex, [(Ph3P)3RhCl], a
Wilkinson catalyst - hydrogenation of alkenes.
• Articles can be electroplated with silver and gold much more
smoothly and evenly from solutions of the complexes, [Ag(CN)2]–
and [Au(CN)2]– than from a solution of simple metal ions.
• In black and white photography, the developed film is fixed by
washing with hypo solution which dissolves the non decomposed
AgBr to form a complex ion, [Ag(S2O3)2]3– .
• Prussian blue – Mixture of hexacyanoFe(II) and Fe(III) -
Fe4[Fe(CN)6]3 inks, blueprinting, cosmetics, paints (commercial
coloring agents)
▪ History of Prussian blue:
The first modern, artificially manufactured colour was Prussian blue. It was
made by the colormaker Diesbach of Berlin in about 1704. Diesbach
accidentally formed the blue pigment when experimenting with the oxidation
of iron. The pigment was available to artists by 1724 and was extremely
popular throughout the three centuries since its discovery.
Hardness of water
❖ Hardness of water is estimated by

titration with the sodium salt of EDTA.
❖ During titration, the calcium and
magnesium ions in hard water form the
stable complexes, Calcium EDTA and
Magnesium EDTA.
❖ Hardness of water is estimated by
simple titration with Na2EDTA.
❖ The selective estimation of these ions
can be done due to difference in the
stability constants of calcium and
magnesium complexes.
Representative Metal Complexes in Catalysis
• Zeise’s Salt : K[Pt(C2H4)Cl3]

• Magnus Green Salt : [Pt(NH3)4][PtCl4]
• Edman’s Salt : K[Co(NH3)2(NO2)4
• Reinecke’s Salt : NH4[Cr(NH3)2(NCS)4]
• Vaska’s Complex : [Ir(CO)(PPh3)2Cl]
• Wilkinson’s Catalyst : [Rh(PPh3)3Cl]
Organometallics – Introduction, stability, structure and
applications of metal carbonyls, ferrocene and Grignard
reagent
28
What are Organometallics?
❖ An area which bridges organic and inorganic chemistry.
❖ A branch of coordination chemistry where the complex has one or more
metal-carbon bonds.
C always is more electronegative compared to M.

❖ The leading journals of the field define an "organometallic" compound as one in which there is a
bonding interaction (ionic or covalent, localized or delocalized) between one or more carbon atoms of
an organic group or molecule and a main group, transition, lanthanide, or actinide metal atom (or
atoms)
❖ Following longstanding tradition, organic derivatives of metalloids such as boron (B), silicon (Si),
germanium (Ge), arsenic (As), tellurium (Te) are also included in this definition.
Zeise’s Salt- The first transition metal ❖ Discovery 1827
organometallic compound: ❖ Structure ~ 150 years later
First σ-bonded Organometallic Compound- Diethyl Zinc:

3 C2H5I + 3 Zn → (C2H5)2Zn + C2H5ZnI + ZnI2
29
First organometallics in homogeneous catalysis- The Hydroformylation (1938)
First Industrial plant-

hydroformylation
detergents
30
Why are organometallics important?
❖ Are we dealing with ‘a’ special element?
❑ What is special about carbon?
• Forms bonds with other carbon atoms (C-C)
readily and they are strong (catenation)
• Forms strong multiple bonds (C=C)
• Forms very strong bonds with another special
element H!!
• Cyclic “C=C-C” fragments would be extra
stable - AROMATIC
❑ C and its electronic configuration!
1s2 2s2 2p2
❑ Why is this special ?
• To form a full shell, it would require 4 covalent bonds
• Gap between the 2s and 2p is just right!
• 1s2 2s1 2px12py12pz1
• When 4 equivalent covalent bonds are formed, no extra electrons / no vacant
31
orbitals
Organic vs Organometallic reactivity
Organic chemistry Organometallic chemistry
▪ C is the negative end of the M-C bond

("umpolung")
▪ C-C/C-H bonds are covalent ▪ Reactivity dominated by nucleophilic
▪ Cδ+-Xδ- : polar (partly ionic) attack on metal atom and electrophilic
▪ Reactivity dominated by nucleophilic attack on carbon Atom
attack at carbon atom ▪ Associative and dissociative
▪ SN2 and SN1 like reactivity substitution at M 32
Some Important Ligand Nomenclature
“eta-x” was originally developed to indicate how many carbons of a π-system were
ηx coordinated to a metal center. Hapticity is another word used to describe the bonding
mode of a ligand to a metal center. An η5-cyclopentadienyl ligand, for example, has all
five carbons of the ring bonding to the transition metal center.
• ηx values for carbon ligands where the x value is odd usually indicate anionic carbon ligands
(e.g., η5-Cp, η1-CH3, η1-allyl or η3-allyl, η1-CH=CH2)
• The # of electrons donated (ionic method of electron counting) by the ligand is usually
equal to x + 1
• Even ηx values usually indicate neutral carbon π-system ligands (e.g., η6-C6H6, η2-
CH2=CH2, η4-butadiene, η4-cyclooctadiene)
• Number of electrons donated by the ligand in the even (neutral) case is usually just equal to x.
η5-Cp η3-Cp η3-allyl η1-allyl 33

µx “mu-x” is the nomenclature used to indicate the presence of a bridging ligand
between two or more metal centers. The x refers to the number of metal centers
being bridged by the ligand. Usually, most authors omit x = 2 and just use μ to
indicate that the ligand is bridging the simplest case of two metals.
❖ bridging ligands are usually placed next to the metals, then followed by the other ligands:
Co2(μ-CO)2(CO)6, Rh2(μ-Cl)2(CO)4, Cp2Fe2(μ-CO)2(CO)2
34
❖Organometallic compounds are classified into three classes.
• (i) Sigma (σ) bonded organometallic compounds: In these complexes, the metal atom and
carbon atom of the ligand are joined together with a sigma bond,
For Example:
• (a) Grignard reagents, R–Mg–X where R is an alkyl or aryl group, and X is a halogen.
• (b) Zinc compounds of the formula R2Zn such as (C2H5)2Zn
• Other similar compounds are (CH3)4Sn, (C2H5)4Pb, Al2(CH3)6, Al2(C2H5)6, Pb(CH3)4 etc.
Al2(CH3)6 is a dimeric compound and has a structure similar to diborane, (B2H6). It is an
electron deficient compound, and two methyl groups act as bridges between two aluminium
atoms.
(ii) Pi (π) bonded organometallic compounds:

These are the compounds of metals with alkenes,
alkynes, benzene and other ring compounds. In
these complexes, the metal and ligand form a
bond that involves the π-electrons of the ligand.
Three common examples are Zeise’s salt,
ferrocene and dibenzene chromium. These are
shown below.
(iii) Sigma and π-bonded organometallic compounds
• Metal carbonyl compounds formed between metal and carbon monoxide,

belong to this class. These compounds possess both σ-and π-bonding.
Generally, oxidation state of metal atoms in these compounds is zero.
Carbonyls may be mononuclear, bridged or polynuclear.
Stability of Organometallic Compounds
❖ In general terms, the stability of an organometallic compound may refer to either its
thermal stability, or resistance to chemical attack (by air and moisture). Obviously,
these different types of stabilities would depend both on thermodynamic as well as
kinetic factors.
The organometallic compounds are generally hydrolysed via nucleophilic

attack by water, which is facilitated by:
(1) the presence of empty low-lying orbitals on the metal
(2) the polarity of metal-carbon bonds. Rate of hydrolysis is dependent on M-C
bond polarity – greater the polarity, faster will be the rate
37
Thermal Stability
The thermodynamic stability of a compound relative to its constituent elements would
obviously depend upon the standard free energies of formation, ΔG°f values for
organometallic compounds, one has to rely on the known standard enthalpies of
formation, ΔH°f, making due allowance for plausible estimates for the contributions of ths
entropy terms TΔS, in the well-known relationship:
ΔG = ΔH ─TΔS
For example, let us for the purpose of simplicity consider that tetramethyllead
decomposes into lead, decomposes into lead, methane and ethane only, i.e.,
Pb(CH3)4 (g) → Pb(s) + 2CH4(g) + C2H4(g)

ΔH°f (kj/mol) +137 0 2×(-73) +52
The standard enthalpy change ΔHm for this reaction would be given by the difference
between the standard enthalpies of formation, ΔHf, for the products and reactants, i.e.,
ΔHm = ─146+52─137 = ─231 kj mol─1 38
Factors influencing the stability/ reactivity of Organometallics
❖ The thermodynamic stability of metal-alkene complexes is strongly affected by the nature of
the alkene (and metal):
• 1) Electron-withdrawing groups on the alkene generally increase the strength of the
metal-alkene bonding, while electron-donating groups generally decrease the stability.
• 2) In cases where cis-trans isomerism is possible, the more stable complex is almost always
formed by the cis-alkene (steric factors).
• 3) Presence of β-hydrogen in the alkyl chains attached to the metal
▪ The main driving force for β-hydride elimination is the
formation of a stronger M-H bond (almost always stronger
than M-alkyl) and the generation of an alkene ligand that
reduces the unsaturation of the metal complex. The
reverse reaction, however, also can occur and is called a
migratory insertion.
▪ In order to prepare stable M-alkyl complexes one,
therefore, often needs to stay away from alkyls with β-
hydrogens (or avoid metals with empty coordination
39
4. Metal complexes of ring-strained cycloalkenes (e.g., cyclopropene) display higher than
expected stability. The ring strain raised the energy of the cycloalkene ring system making it a
better donor to the metal center (better orbital energy matching). See the next section on
cyclobutadiene for a particularly remarkable example.
Cyclic conjugated π-systems are aromatic if the number of π-electrons equals 4n + 2 (where n
= an integer). Cyclobutadiene is an anti-aromatic since it has 4 π-electrons. The anti-
aromaticity combined with the ring strain makes this simple molecule too unstable to exist as a
free organic compound.
The high stability of a cyclobutadiene coordinated to a metal arises from the mixing of the 4 π
electrons on the cyclobutadiene with one of the metal d orbitals that has 2 e- and the right
symmetry to mix in and form a 6 π electron aromatic system!
40
5. Chelating dienes show the expected stabilization from the chelate effect. The
most common examples are norbornadiene and cyclooctadiene shown below.
Note that these can still be easily substituted off the metal by stronger
coordinating ligands such as phosphines.
41
The 18-electron Rule or Effective atomic number (EAN)
❖ The 18e rule is a way to help us decide whether a given d-block transition metal organometallic
complex is likely to be stable. Not all the organic formulas we can write down correspond to
stable species. Recall: Second row elements (B, C, N, O, F) have 4 valence orbitals (1s + 3p) so
they can accommodate up to 8 valence electrons--the octet rule.
▪ For example, CH5 requires a 5-valent carbon and is therefore not stable. Stable compounds,
such as CH4, have the noble gas octet, and so carbon can be thought of as following an 8e rule.
▪ The 18e rule, which applies to many low-valent transition metal complexes, follows a similar line
of reasoning. The metal now has one s, and three p orbitals, as before, but now also five d
orbitals. We need 18e to fill all nine orbitals; some come from the metal, the rest from the ligands.
Therefore, we can expect that the low-lying MOs can accommodate up to 18 valence electrons--
The 18-Electron Rule.
❖ The rule states that “thermodynamically
stable transition metal organometallic
compounds are formed when the sum of the metal d electrons and the
electrons conventionally considered as being supplied by the surrounding
ligands equals 18”
42
Counting electrons for metal complex
To count the electrons of a metal complex, one must:
a) note any overall charge on the metal complex
b) know the charges of the ligands bound to the metal center (ionic ligand method)
c) know the number of electrons being donated to the metal center from each ligand (ionic
ligand method)
Similarly for a transition metal complex, the electron count is the sum of the metal valence
electrons + the ligand centered electrons.
❖ Covalent Model: # e = # metal electrons (zero valent) + # ligand electrons - complex charge
Metal: The number of metal electrons equals its column number (i.e., Ti = 4e, Cr = 6e, Ni =
10e)
Ligands: In general L donates 2 electrons, X donates 1 electron.
❖ Ionic Model: # e = # metal electrons (dn) + # ligand electrons

Metal: Determined based on the number of valence electrons for a metal at the oxidation state
present in the complex
Ligands: In general and L and X are both 2 e donors.
❖ Complexes with 18 e- counts are referred to as saturated. 43
❖ Complexes with counts lower than 18e- are called unsaturated.
Electron Counting ❖ Step 2: Determine the d electron count.
Recall: subtract the metal's oxidation state from
❖ Step 1: Determine the oxidation state of the its group #.
metal. To do this, balance the ligand charges
with an equal opposite charge on the metal. This
is the metal's formal oxidation state. ❖ Step 3: Determine the
• To determine ligand charges, create an ionic electron count of the
model by assigning each M-L electron pair to the complex by adding the #
more electronegative atom (L). This should result of electrons donated by
in stable ligand species or ones known as each ligand to the metal's
reaction intermediates in solution. d electron count.
44
Example 1
Please note that we are using the Ionic Method of electron-counting. 95% of
inorganic/organometallic chemists use the ionic method. The ionic method
assigns formal charges to the metal and ligands in order to keep the ligands
with an even # of electrons and (usually) a filled valence shell. Synthetically,
the ionic method generally makes more sense and the one that we will use in
this course.
1) There is no overall charge on the complex

2) There is one anionic ligand (CH3−, methyl group)
3) Since there is no overall charge on the complex (it Now we can do our electron counting:
is neutral), and since we have one anionic ligand Re(+1) d6
present, the Re metal atom must have a +1 charge to 2 PR3 4e-
compensate for the one negatively charged ligand. 2 CO 4e-
The +1 charge on the metal is also its oxidation state. CH3− 2e-
So the Re is the in the +1 oxidation state. We denote CH2=CH2 2e-
I
this in two different ways: Re(+1), Re(I), or Re .
Total: 18e- 45
HMn(CO)5
Mn(+1) d6 6e-
5 CO 10e-
H− 2e-
Total: 18e-
46
Metal-Carbonyls
As one goes from a terminal CO-

bonding mode to μ2-bridging and
finally μ3-bridging, there is a relatively
dramatic drop in the CO stretching
frequency seen in the IR.
❖ Standard Bonding Modes
2e- neutral donor 2e- neutral donor 3e- neutral donor

47
Three types (two of which are important) of CO-Metal bonding interactions
❖Formation of σ-bond:
▪ The overlapping of empty hybrid orbital on metal atom with the filled hybrid orbital on carbon
atom of carbon monoxide molecule through lone pair electrons results into the formation of a
M←CO σ-bond.
❖Formation of π-bond by back donation:
▪ This bond is formed because of overlapping of filled dπ orbitals or hybrid dpπ orbitals of metal
48
atom with antibonding pi orbitals on CO molecule.
Structure of Ni(CO)4
49
Ligand Donation Effects
The ability of the ligands on a metal to donate electron density to the metal center certainly has
considerable effect on the absolute amount of electron density on that metal. This, in turn, naturally
effects the νCO IR stretching frequencies in metal carbonyl complexes. Ligands that are trans to a
carbonyl can have a particularly large effect on the ability of the CO ligand to effectively π-
backbond to the metal. For example, 2 trans π-backbonding ligands will partially compete for the
same d-orbital electron density, weakening each others net M-L π-backbonding.
When the trans ligand is a σ-donating ligand, this can increase the M-CO bond strength (more
M=C=O character) by allowing unimpeded metal to CO π-backbonding. Pyridine and amines are
not that strong σ-donors, but they are even worse π-backbonding ligands. So the CO has virtually
no competition for π-backdonation. Based on CO IR stretching frequencies, the following ligands
can be ranked from best π-acceptor to worst:
NO+ > CO > PF3 > RN≡C > PCl3 > P(OR)3 > PR3 > RC≡N > NH3 50
σ/π Bridging CO
This is where the CO not only acts as a traditional σ-donor/π-acceptor to

one or more metal centers, but also as a π-donor to additional metals. This
will occur for more electron deficent metal complexes where the metal
centers have less need to π-backbond to the carbonyl, but have the empty
orbitals to accept electron density from the carbonyl π-system. The CO
ligand here can act as a 4 or 6 electron donor!
2. Determination of Bond orders
Applications
• It has been seen that I.R. absorption frequency of ligated
1. Determination of geometries of Carbonyls CO is directly proportional to its B.O. In other words, the
through calculating number of IR active I.R. absorption band due to the stretching vibration of
bands ligated CO with a higher B.O. would occur at a higher
frequency and the I.R. absorption band of ligated CO with
a lower B.O. would occur at a lower frequency. Since the
absorption frequency for free CO is equal to 2250 cm─1
while that for ligated CO lies between 2220-1700 cm─1,
ligated CO has lower B.O. The lower B.O. is due to the
transfer of metal dπ electrons into the π* orbitals of ligated
CO. Let us study the following examples.
• Since the presence of positive charge on [Mn(CO)6]+
resists the flow of metal dπ electrons into the π* orbitals of
CO, the B.O. of CO increases. Due to the increase in B.O.,
the absorption band of ligated CO occurs at higher
frequency (= 2090 cm─1)
Metal Carbonyl [V(CO)6]─ [Cr(CO)6]─ [Mn(CO)6]+

Charge on Metal -1 0 +1
Absorption frequency for CO (cm─1) 1860 1980 2090 52
3. To differentiate between terminal and bridging carbonyl groups
4. To study reaction rates

The measurement of the rates of disappearance of the intensity of CO absorption bands in the I.R.
spectra can be used to study the rates of substitution reaction of metal carbonyls
5. Ligand Metal carbonyls are useful in organic synthesis and as catalysts or catalyst
6. Precursors in homogeneous catalysis, such as hydroformylation and Reppe chemistry.
H2 + CO + CH3CH=CH2 → CH3CH2CH2CHO
Dicobalt octacarbonyl acts as catalyst.
Co2(CO)8 could be used for hydrosilylation of olefins also.
7. In the Mond process, nickel carbonyl is used to produce pure nickel.
8. In organometallic chemistry, metal carbonyls serve as precursors for the preparation of other
53
ogranometallic complexes.
Other Applications
Metal carbonyls are used in several industrial processes. Perhaps the earliest
application was the extraction and purification of nickel via nickel tetracarbonyl by the
Mond process.
❖Fe(CO)5 is used inter alia for the preparation of inductors, pigments, as dietary
supplements in the production of radar-absorbing materials in the stealth technology,
and in thermal spraying.
❖Metal carbonyls are used in a number of industrially important carbonylation
reactions. In the oxo process, an alkene, hydrogen gas, and carbon monoxide react
together with a catalyst (such as HCo(CO)4) to give aldehydes.
❖ Several other Metal-Carbonyl complexes have been employed in the
hydrocarboxylation and hydrogenation reactions.
54
Structure and Bonding Ferrocene
• Mössbauer spectroscopy indicates that the iron center in
ferrocene should be assigned the +2 oxidation state.
Each cyclopentadienyl (Cp) ring should then be
allocated a single negative charge. Thus ferrocene
could be described as iron(II) bis(cyclopentadienide)
Fe2+[C5H5- ]2.
• The number of π-electrons on each ring is then six,
which makes it aromatic according to Hückel's rule.
These twelve π-electrons are then shared with the metal
via covalent bonding. Since Fe2+ has six d-electrons, the
complex attains an 18-electron configuration, which
accounts for its stability. In modern notation, this
sandwich structural model of the ferrocene molecule is
denoted as Fe(η5-C5H5)2.
• Crystallography reveals that the cyclopentadienide
rings are in staggered conformation.
• Hybridization: d2sp3
• Magnetic Nature: Diamagnetic 55
Applications of Ferrocene
1. Fuel additives: Ferrocene and its derivatives could be used as antiknock agents in the fuel
for petrol engines. They are safer than previously TEL.
1. Pharmaceutical: Ferrocene derivatives have been investigated as drugs e.g. one drug has
entered clinic trials, Ferroquine (7-chloro-N-(2-((dimethylamino)methyl)ferrocenyl)quinolin-4-
amine), an antimalarial. Ferrocene-containing polymer-based drug delivery systems have
been investigated.
1. Solid rocket propellant: Ferrocene and related derivatives are used as powerful burn rate
catalysts in ammonium perchlorate composite propellant.
1. As a ligand scaffold: Chiral ferrocenyl phosphines are employed as ligands for transition-
metal catalyzed reactions. Some of them have found industrial applications in the synthesis of
pharmaceuticals and agrochemicals.
56
Fuel additive, smoke suppressant and chiral catalyst precursor
Ferrocene powder Ferrocene crystals
Ferox Gas & Diesel Fuel Additive

is a catalyst that is an eco-friendly
fuel additive and horsepower
booster. It allegedly increases
mileage from between 10 and 20%
while also significantly reducing
harmful emissions. 57
The Grignard Reagent
Grignard reagents are formed by the reaction of magnesium metal with alkyl or alkenyl halides.
They’re extremely good nucleophiles, reacting with electrophiles such as carbonyl compounds (aldehydes,
ketones, esters, carbon dioxide, etc) and epoxides.
They’re also very strong bases and will react with acidic hydrogens (such as alcohols, water, and carboxylic
acids).
58
Applications of Grignard reagents ❖ Reaction with esters to give tertiary
❖ Reaction with aldehydes to form alcohols
secondary alcohols
❖ Reaction with epoxides
❖ Reaction with ketones to form tertiary

alcohols
❖ Reaction with CO2 to make carboxylic

acids
59
Metals in biology
Contents……Metals in biology (haemoglobin, chlorophyll-

structure and property)
60
Chlorophyll- Structure and Property
❖ Structure of Chlorophyll
• Chlorophylls are green pigments with polycyclic, planar
structures resembling the protoporphyrin system
present in haemoglobin
• In chlorophyll, Mg2+ is the metal centre
• The four inward-oriented nitrogen atoms of the
porphyrin ring in chlorophyll are coordinated with the
Mg2+
• All chlorophylls have a long phytol side chain, esterified
to a carboxyl-group substituent in ring IV
• Chlorophylls also have a fifth five membered ring not
present in heme
• The heterocyclic five-membered ring system that
surrounds the Mg2+ has an extended polyene structure,
with alternating single and double bonds
• Such polyenes characteristically show strong absorption
in the visible region of the electromagnetic spectrum
• Chlorophylls have unusually high molar extinction
coefficients (higher light absorbance) and are therefore
particularly well-suited for absorbing visible light during 61
photosynthesis
❖ Chloroplasts always contain both chlorophyll a and
chlorophyll b
❖ Both are green, their absorption spectra are sufficiently
different that they complement each other’s range of light
absorption in the visible region
❖ Both chlorophyll a & b absorb in the blue and red region
so that the remaining green region is transmitted – hence
chlorophylls are green in colour
❖ Most plants contain about twice as much chlorophyll a
as chlorophyll b
❖ Chlorophyll is always associated with specific binding
proteins, forming light-harvesting complexes (LHCs) in
which chlorophyll molecules are fixed in relation to each
other, to other protein complexes, and to the membrane.
62
Role of Mg in chlorophyll
❖ Without Mg2+ the chlorin ring is fluorescent –
i.e. the absorbed light energy is emitted back
immediately
❖ With Mg2+ chlorophyll becomes
phosphorescent
❖ In the case of fluorescence, the absorbed
light energy is lost immediately – will not be
used for chemical reaction
❖ In the case of phosphorescence, there will
be excited state of finite life time and the
energy can be used for chemical
reactions
❖ The Mg2+ coordination increase the rigidity
of the planar chlorin ring: The energy loss
as heat due to vibration of the ring during
light absorption is prevented
63
Photosynthesis Reaction
Two types of photosystems

cooperate in the light reactions 64
A Photosynthesis Road Map
Nicotinamide Adenine Dinucleotide Phosphate

Hydrogen (NADPH)
Adenosine 5'-triphosphate (ATP)
65
Hemoglobin Hb
Hb is not an exact Four units of Hb

tetramer of Mb
3 major types of Hb
Hb A (Adult)
Hb F (Fetal)
Hb S (Sickle cell)
66
❖ Each of these subunit polypeptides contains a heme
group—an iron atom at the center of a poryphyrin
ring—which reversibly binds a single O2 molecule in
the ferrous state (Fe2+).
❖ Whereas free heme binds O2 irreversibly and is

converted to the ferric state (Fe3+) in the process, Hb
can reversibly bind O2 because the valence state of
the iron atom is protected by encapsulating the heme
in the globin protein fold
❖ Each tetrameric (α2β2) Hb can therefore reversibly

bind four O2 molecules.
❖ Oxygenation changes the electronic state of the Fe2+

heme iron, which is why the color of blood changes
from the dark, purplish hue characteristic of venous
blood to the brilliant scarlet of arterial blood. 67
❖ The organic component of the heme group—
the protoporphyrin—is made up of four pyrrole
rings (A, B, C & D) linked by methine bridges
to form a tetrapyrrole ring. Four methyl
groups, two vinyl groups, and two proprionate
side chains are attached.
❖ The iron atom at the center of the
protoporphyrin is bonded to the four pyrrole
atoms.
❖ Under normal conditions the iron is in the
ferrous (Fe2+) oxidation state. The iron atom
can form wo additional bonds, one on each
side of the heme plane, called the fifth and
sixth coordination sites.
❖ The fifth coordination site is covalently bound
by the imidazole side chain of the globin chain
(the “proximal histidine,” α87 and β92).
❖ The sixth coordination site of the iron ion can
bind O2 or other gaseous ligands (CO, NO,
❖ CN−, and H2S
68
▪ Role of distal
histidine: Makes O2
to bind in a bent
fashion and makes it
difficult for CO to
bind in a linear
fashion.
▪ An isolated heme
binds CO 25000 times
as strongly as O2 in
solution. In the living
system binding affinity
for oxygen is reduced
considerably. For CO
to bind strongly, it has
Tense (T) state Relaxed (R) state
to bind linearly which
is made difficult by
distal histidine
69
Module-3
Organic intermediates and reaction transformations
Contents…. (6 h)
Organic intermediates - stability and structure of carbocations, carbanions
and radicals; (2 h)
Aromatics (aromaticity) and heterocycles (3, 4, 5, 6 membered and fused
systems); (2 h)
Organic transformations for making useful drugs for specific disease targets
(two examples) and dyes. (2 h)
1
Organic Reaction Intermediates
❖Most of the organic reactions occur via a specific chemical species (intermediate) which
is extremely reaction and short – lived (10-6 second to a few seconds). Isolation of such
species is a difficult task.
❖These reactive intermediates can have the valency of carbon atoms either 2 or 3.
❖ Examples of such reaction intermediates are carbocations, carbanions, free radicals,
carbenes and nitrenes – and they are quickly converted into more stable molecules.
❖ However, fairly stable organic intermediates have been prepared such as carbenes
and carbocations.
❖ Among all the intermediates, only carbanions have a complete octet around the
carbon.
❖ There are many other organic ions and radicals with charges and unpaired electrons
on atoms other than carbon, they are nitrenes- the nitrogen analogs of carbenes. 2
Carbocations
Organic species having a positively charged carbon atom bearing only six bonded electrons are called
carbocations. For example:
Structure:
❖ The carbon atom with a positive charge is referred as carbocation (or carbonium ion) and it
belongs to sp2 hybridization.
❖ The three sp2 hybridized orbitals are utilized in making bonds to three substituents.
❖ In order to minimize repulsion between the bonding electron pairs (i.e. to afford maximum separation of
these electron pairs) a carbocation possesses a planar configuration with bond angles of
120o. The empty p orbital is perpendicular to the plane.
❖Carbocations are extremely reactive species due to their ability to complete the octet of
3
the electron-deficient carbon.
Classification of Carbocations
Carbocations are classified as primary (1o), secondary (2o), and tertiary (3o) on the basis of number of carbon
atoms (one, two, or three) directly attached to positively charged carbon. For example:
The factors responsible for carbocation stability are –

(i) Inductive effect, (ii) Hyperconjugative effect, (iii) Resonance effect, (iv) Steric effect and
(v) Constituting an aromatic system.
(i) Inductive effect
❖ A charge-dispersing factor stabilizes an ion.
❖ The electron-releasing inductive effect (+I) exerted by an alkyl group attached to the positive
carbon of a carbocation neutralizes the charge partially.
❖ As a consequence, the charge becomes dispersed over the alkyl groups and the system becomes
stabilized.
❖ For example, the methyl groups in isopropyl cation stabilize the system through their +I effects.
❖ The stability of carbocations increases with increasing the number of alkyl groups attached to the
4
positive carbon.
(ii) Hyperconjugative effect
❖ An alkyl group may reduce the positive charge of a carbocation by hyperconjugative electron- release.
❖ The charge becomes dispersed over the α-hydrogens and consequently, the system becomes stabilized.
Hyperconjugation in ethyl cation, for example, occurs as follows
❖ As the number of α-hydrogens, i.e., the number of hyperconjugative forms increases, the stability of carbocations
increases. Hence, the order of stabilities of methyl substituted carbocations is ::
(iii) Resonance effect

❖ Resonance is a major factor influencing the stability of
carbocations.
❖ When the positive carbon of a carbocation is next to a double bond,
effective charge delocalization with consequent stabilization occurs.
❖ Allyl and benzyl cations, for examples, are found to be highly
stabilized by resonance. 5
(iv) Steric effect
❖ Steric effect causes an increase in stability of tertiary
carbocations having bulky alkyl groups.
❖ For example, the substituents in tri-isopropyl cation (having
planar arrangement with 120° angles) are far apart from each
other and so there is no steric interference among them.
❖ However, if this carbocation is added to a nucleophile, i.e., if a
change of hybridization of the central carbon atom from sp2
(trigonal) to sp3 (tetrahedral) takes place, the bulky isopropyl
groups will be pushed together.
❖ This will result in a steric strain (B strain) in the product
molecule. Because of this, the carbocation is much reluctant to
react with a nucleophile, that is, its stability is enhanced due to
steric reason.
(v) Constituting an aromatic system

❖ The vacant p orbital of a carbocation may be involved in constituting a planar (4n +2)π electron system. where n =
0,1,2.... etc., i.e., a carbocation may be stabilized by constituting an aromatic system.
❖ Cycloheptatrienyl cation, for example, is unusually stable because it is a planar 6π electron system and aromatic.
6
Reaction of Carbocations
Question: Arrange the following carbocations in order of their increasing stability and provide
reason.
❖ The carbocation I is stabilized by the +I effects of three -CH3 groups

and hyperconjugative effect involving nine C-H bonds.
❖ The carbocation III is similarly stabilized by +I effect of three ring
bonds.
❖ However, it is not stabilized by hyperconjugation because formation
of a double bond at the bridgehead position is not possible (Bredt's Hence, the order of their increasing stability is:
rule).
❖ Again, the carbocation suffers from angle strain because the angle
between bonds is somewhat less than the sp2 bond angle, i.e., 120".
❖ The carbocation II is the most stable one because it is highly
stabilized by resonance and also by both inductive and
hyperconjugative effects of two methyl groups.
10
Carbanions
The species containing negatively charged carbon atom is known as

carbanion. For example:
Structure:
❖ The central carbon atom of a carbanion is sp3 hybridized.
❖ It is surrounded by three bonding pairs and one unshared pair of electrons which occupies an sp3 orbital. Thus, a
carbanion is expected to have the tetrahedral shape.
❖ However, the shape is not exactly that of a tetrahedron. It is found to have the pyramidal shape.
❖ Since the repulsion between the unshared pair and any bonding pair is greater than the repulsion between any two
bonding pairs, the angle between two bonding pairs (i.e., two sp3- σ bonds) is slightly less than the normal tetrahedral
value of 109.5° and because of this, a carbanion appears to be shaped like a pyramid with the negative carbon at the
apex and the three groups at the corners of a triangular base.
❖ However, the resonance-stabilized carbanions, such as allylic and benzylic carbanions are sp2 hybridized and they
assume trigonal planar structure. 11
The factors responsible for carbanion stability are -
The structural features responsible mainly for the increased stability of carbanions are :
(i) the amount of ‘s’ character of the carbanion carbon atom,
(ii) inductive electron withdrawal,
(iii) conjugation of the non-bonding electron pair with an unsaturated system, and
(iv) constituting an aromatic system.
(i) The amount of ‘s’ character of the carbanion carbon atom

❖ An s orbital is closer to the nucleus than the p orbital in a given main quantum level and it possesses lower energy.
❖ An electron pair in an orbital having large s character is, therefore, more tightly held by the nucleus and hence of
lower energy than an electron pair in an orbital having small s character.
❖ Hence, a carbanion at an sp hybridized (50% s character) carbon atom is more stable than a carbanion at a sp2
hybridized (33.33% s character) carbon atom, which in turn is more stable than a carbanion at an sp3 hybridized
(25% s character) carbon atom. Thus, the order of carbanion stability is:
(ii) Inductive electron withdrawal

❖ Groups having electron-withdrawing inductive effects (H) stabilize a carbanion by
dispersing the negative charge.
❖ In a nitrogen ylide, for example, the carbanion is stabilized by the -I effect of the adjacent
12
positive nitrogen.
(iii) Conjugation of a non-bonding electron pair with an
unsaturated system
❖ Where there is a double or triple bond α to the carbanion
carbon atom, the anion is stabilized by delocalization of its
negative charge with the t orbitals of the multiple bond.
❖ Thus, allylic and benzylic carbanions and the carbanions
attached to the functional groups such as -NO2, -C≡N,
>C=O, etc. are stabilized by resonance.
(iv) Constituting an aromatic system

❖ The unshared pair of a carbanion may be involved in
constituting a planar (4n + 2)π electron system where n = 0, 1,
2... etc., i.e., a carbanion may be stabilized by constituting an
aromatic system
❖ Cyclopentadienyl anion, for example. is unusually stable
because it is a 6π electron system and aromatic.
Question: Give the order of stability of the following simple carbanions :
Because of the destabilizing influence of the electron-donating inductive effect of alkyl groups, the order of stability of
these simple carbanions is as follows:
13
Reaction of Carbanions
Reactions of Carbanions
Question: Arrange the following carbanions in each of the following series in order of increasing stability:
The order of increasing stability of these carbanions is:
❖ The electron-releasing methyl groups of isopropyl anion (I) intensify the negative charge on carbon and make it less stable than
methyl anion (III) where there is no possibility of charge intensification.
❖ The external orbitals (orbitals directed to the outside bonds) in cyclopropane have larger (33%) s character i.e., they are
approximately sp2 orbitals. Because of this, the unshared pair in cyclopropyl anion (IV) is more tightly held with the carbon nucleus
than the electrons in methyl anion (III) that occupies an sp3 orbital (25% s character). Consequently, the former anion is more stable
than the latter.
❖ In vinyl anion (VI), the unshared pair occupies an sp orbital (33.33% s character) and so this anion is somewhat more stable than
cyclopropyl anion (IV).
❖ The charge in allyl anion (II) is delocalized by resonance with the adjacent double bond and so it is more stable than vinyl anion (VI)
in which the charge is localized.
❖ Since the unshared pair in cyclopentadienyl anion (V) is involved in forming an aromatic system, charge delocalization and
consequent stabilization is far greater for this anion than for allyl anion. 17
Radicals
❖ Homolytic cleavage of covalent bonds leads to the formation of neutral
species possessing an unpaired electron. These are known as free radicals.
❖ Free radicals containing odd electrons on carbon atoms are collectively
called carbon radicals or simply free radicals. For example, methyl radical
(ĊH3 ), phenyl radical (Ph⋅), etc.
❖ They are classified as primary, secondary, and tertiary free radicals
according to the number of carbon atoms (one, two or three) directly
attached to the carbon atom bearing the unpaired electron.
❖ For example, ethyl radical (CH3ĊH2) is a primary, isopropyl radical
(Me2ĊH) is a secondary and tertbutyl radical (Me3Ċ) is a tertiary radical.
Stability:
(i) Hyperconjugation: Free radicals become stabilized by hyperconjugation involving α-H atoms
❖ As the number of α-H atoms increases, hyperconjugation becomes more effective and consequently, the radical
becomes more stabilized.
❖ The relative stability of simple alkyl radicals is found to follow the sequence
(most stable) R3Ċ (tertiary) > R2ĊH (secondary) > RĊH2 (primary) > ĊH3 (methyl) (least stable).
❖ For example, tert-butyl radical, Me3Ċ (with nine hyperconjugable α-H atom) is more stable than isopropyl radical,
Me2ĊH (with six hyperconjugable α-H atom) which in turn is more stable than ethyl radical, MeĊH2 (with only three
hyperconjugable α-H atom). The methyl radical, ĊH3 is least stable because the unpaired electron is not18 at all
delocalized.
(ii) Resonance:
❖ Resonance is a major factor influencing the stability of free radicals.
❖ When the carbon bearing the odd electron is α- to a double bond,
effective delocalization of the unpaired electron with the π orbital system
with consequent stabilization occurs.
❖ Allyl and benzyl radicals, for example, are found to be particularly stable
because of resonance.
(iii) Steric Strain:

❖ Another factor responsible for the increased stability of tertiary radicals is steric.
❖ There occurs considerable relief of steric strain when a sp2 hybridized tertiary radical is formed from an sp3
hybridized precursor and this is because repulsion between the bulky alkyl groups is relieved to a certain extent by
an increase in bond angles from 109.5° to about 120°.
❖ Thus, the radical is much reluctant to react further, i.e., its stability is enhanced due to steric reason.
19
Reactions of Free Radicals
Aromaticity (2h)
(Definition, Criteria, aromatic, nonaromatic, antiaromatic,
heterocyclic compounds)
Drugs (1h)
(Aspirin, Paracetamol- Synthesis and uses)
Dyes (1h)
(Methyl orange, Indigo- Synthesis and uses)
Aromaticity
• Aromaticity was associated with a specific chemical reactivity

(substitution reactions in preference to addition).
• Aromaticity is now generally associated with the property of special
stability of certain completely conjugated cyclic and planar
molecules.
• A major contribution to the stability of aromatic systems comes from
the delocalization of electrons (which also imparts diamagnetic ring
current).
• Hückel molecular orbital (HMO) theory states that planar
monocyclic completely conjugated hydrocarbons will be aromatic
when the ring contains 4n+2 π electrons (Huckel’s Rule).
Criteria of aromaticity
•
Aromatic compounds: Molecules which obey all the 4 rules.
Non-aromatic compounds: Molecules which follow these 4 rules partially i.e. non-cyclic, non-planar, or do
not hold a comprehensive conjugated π system inside the ring.
Anti-aromatic compounds: Exclusively do not follow Huckel’s rule.
4n+2 (n = 0)= 2 π electrons
Cyclic
Non Planar
Not Conjugated
Follow Huckel’s rule
Non Aromatic
Cyclic
Planar
Conjugated
Aromatic
Stability Order: Aromatic > Nonaromatic > Antiaromatic

* 4n+2 (n = 1)= 6 π electrons
Cyclic
Planar
Conjugated
Aromatic
Cyclic
Non Planar
Non Conjugated
Cycloheptatriene Non Aromatic
* 4n+2 (n = 2)= 10 π electrons
Cyclic
Planar
Cyclic Conjugated
Non Planar Follow
Conjugated Huckel’s rule
Follow Huckel’s Aromatic
rule
Non aromatic
* 4n+2 (n = 3,4)= 14 and 18 π electrons

Cyclic
Planar
Conjugated
Follow Huckel’s
rule
Aromatic
* 4n (n=1) = 4 π electrons
Cyclic
Planar
Conjugated
Do not Follow
Huckel’s rule
Antiaromatic
Cyclic
Non Planar
Non Conjugated
Do not Follow Huckel’s rule
Non aromatic
* 4n (n = 2)= 8 π electrons
Cyclooctatetraene is more Cyclic
flexible than Non Planar
cyclobutadiene and it Conjugated
assumes a non-planar ‘tub Do not Follow Huckel’s rule
shaped’ conformation that nonaromatic due to non
avoids most of the planarity
overlapping between p-
orbitals.
* 4n (n = 3,4)= 12 and16 π electrons
Cyclic Cyclic
Planar Non Planar
Conjugated Conjugated
Do not Follow Huckel’s rule Do not Follow Huckel’s rule
Antiaromatic non aromatic
Characteristics of 3-Membered Ring Heterocyclic Compounds
Cyclic,
Conjugated sp2 hybridised carbons
4 π elections ( 4n rule)
Anti-aromatic
• Cyclic
• no conjugated sp2 hybridised carbons
• Non-aromatic 30
Characteristics of 4-Membered Ring Heterocyclic Compounds
• While counting the number of π-

electrons, first count the electrons
Cyclic which are delocalized over the ring.
Conjugated sp2 • In this case, nitrogen lone pair is
hybridised carbons localised in an sp2 orbital (red) which
4 π elections ( 4n is orthogonal to the π system (blue)
rule) and does not participate in
Anti-aromatic resonance.
2H-OXETEN 2H-THIETEN
• Non-aromatic
• Cyclic
• no conjugated sp2 hybridised
carbons
31
Five Membered Heterocycle: Pyrrole
32
Six Membered Heterocycle: Pyridine
• Pyridine replaces the CH of benzene by an N atom with a
lone pair of electrons and hybridization is sp2 with
similar resonance stabilization energy.
• Lone pair of electrons does not involve in aromaticity.
• Pyridine is a weak base.

• Pyridine is π-electron deficient.
• Electrophilic aromatic substitution is difficult.
• Nucleophilic aromatic substitution is easy.
Resonance energy
of some of the
aromatic systems
Fused Heterocyclic Compounds

• Aromatic due to 10 π-electrons
• Benzene part is non-reactive
• Electrophilic aromatic substitution occurs at the 3-position.
Questions ?
34
Synthetic Route of Aspirin
In the year of 1897, Bayer laboratory gave acetyl salicylic acid the name of Aspirin. Aspirin is one of the safest and
most effective medicines and is extensively used medications globally, which is displayed on the WHO’s List of
Essential Medicines.
• Synthesis of aspirin is an esterification reaction of salicylic
acid and acetic anhydride with an acid catalyst (sulfuric
or phosphoric acid).
Mechanism of Aspirin Synthesis

Uses of Aspirin/Acetylsalicylic acid-(C9H8O4)
❖ Used as an inhibitor of cyclooxygenase, in the treatment of different types of headaches and to
prevent venous and arterial thrombosis.
❖ Useful as an anti-inflammatory agent for long-term as well as acute inflammation; gained a
reputation for treating cardiovascular and cancer.
❖ It is a first-line treatment for the fever and joint-pain symptoms of acute rheumatic fever and
Kawasaki disease.
❖ Similarly, used as an intermediate and raw material in producing other medicines or chemical
compounds like 4-hydroxycoumarin.
Synthetic Route of
Paracetamol
Mechanism of Paracetamol Synthesis

❖Uses of Paracetamol
❖ Antipyretic drugs are used to reduce fever. Paracetamol is a safest antipyretic drug for
children and pregnant women.
❖ An analgesic is a pain-reducing or relieving remedy. Paracetamol is an analgesic drug
without any significant anti-inflammatory effects.
❖ It's available combined with other painkillers and anti-sickness medicines.
❖ It's also an ingredient in a wide range of cold and flu remedies.
❖ Paracetamol's effects are thought to be related to inhibition of prostaglandin
synthesis.
❖ Paracetamol is readily absorbed from the gastrointestinal tract. 36
Dyes
❖ Dyes are colored organic compounds and they are used to impart the color to
various substances/ materials like fabrics, paper, food, hair and drugs etc.
❖ Based on the solubility in water and/or an solvent, organic colorants fall into two
classes, viz. dyes and pigments.
❖ Mechanistically for dyes, the surface coloration is involved while for pigment, it is
mixed with a polymer before the formation of fiber or molded article.
Textile dyeing process involves the following steps:
❖ Disaggregation of the dye

❖ Exhaustion – dye uptake
❖ Adsorption – transfer of dye from aqueous solution onto fibre surface.
❖ Diffusion – Textile dye is diffused into the fibre.
❖ Fixation – Dye is fixed on to the fibre
37
Example: Turmeric
Example: Alizarin Red

Azo Dyes
Triphenylmethane
Dyes
39
INDIGOTIN DYE
❖ Indigo dye is widely used to color blue jeans.
❖ The chemical in indigo which is responsible for the blue colour is indigotin, which is a
dark blue powder at room temperature and is insoluble in water and ethanol.
❖ It is most soluble in chloroform, nitrobenzene and sulphuric acid. It has a fused nitrogen
heterocyclic structure.
❖ To overcome the solubility problem, the dye is reduced to soluble leucoindigo (known as
'white indigo'), and applied to clothes in this form. When exposed to atmospheric
oxygen it re-oxidises to the insoluble form and regains its colour..
❖ Once the dye is applied to the fabrics, the dye will not be leached out even after several
washings due to its insolubility in water.
43
Synthesis:
44

Engineering Chemistry: Module - 1

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Engineering Chemistry

the quantity of matter or a Properties of a system:

Internal energy (U)

� This is an example of the system doing the work on the surrounding 6

⮚ According to 0th law:

❑ Two physical systems are in

⮚ The 0th law of thermodynamics defines thermal equilibrium

▪ It’s the law of conservation of energy

☻ If mass of the system is 1 g, the heat capacity is

❑ The quantity (U + PV) is called the

❑ Molar heat capacity at constant volume

Heat capacity ratio,

⮚ Isothermal Process (constant temperature)

⇒ For an ideal gas,

▪ If the system does work, the energy

⮚ Reversible isothermal expansion:

▪ Work done by the n moles of gas can be

in an isothermal expansion of a perfect gas)

Where, Stot = S + Ssur concentrates on the change in entropy

☻ Notice the increasing disorder in above processes 17

⇒ All spontaneous process occurring in

▪ A Carnot cycle (named after the French engineer Sadi

⮚ Another statement of the 2nd Law:

⮚ Four stages of Carnot Cycle: A. 1st stroke:

▪ The area enclosed by the four curves represents the net

Efficiency of a heat engine

• Another statement of the 2nd Law:

∙ Energy efficiency of the

→ Thermal devices or thermal machines are one of

⮚ Thermodynamic Temperature ⮚ Free energy and the spontaneity

Gibbs Free Energy

ΔH◦ ΔS◦ ΔG◦

Negative at higher temperatures, positive at lower

Negative at lower temperatures, positive at higher

Positive Negative Always positive

Now, consider another general reaction: aA + bB → cC + dD

⮚ Rate law is a result of experimental observation. You CANNOT look

⮚ The rate constant is independent of the concentrations but depends

Separate concentration and time terms

Rate constants can be determined

Energy is needed to overcome a barrier between initial and final states.

where, k is rate constant, Ea is the activation

described by the Arrhenius equation.

Figure: Schematic diagram to illustrate the

Figure: Schematic diagram to illustrate the homogeneous catalysis.

These chemicals help in attaining the equilibrium more quickly by

(3) Hydrolysis of ester in the presence of acid and alkali:

(4) Hydrolysis of sucrose (cane sugar) into glucose and fructose in

In heterogeneous catalysis the reactions take place at the interface of two

Figure: Schematic diagram to illustrate the heterogeneous catalysis.

Reaction catalysed by the

E + S → ES Rate of formation of ES = ka[E][S]

Step 2: Unimolecular decomposition of the complex:

ES → P + E Rate of formation of S = kb [ES]

Inorganic complexes - structure, bonding and application;

Organometallics – introduction, stability, structure and applications

Metals in biology: haemoglobin and chlorophyll- structure and

3Cl– Fe(CN)2 + 4KCN Fe(CN)2.4KCN

N forms a coordinate covalent bond

❖ Sidgwick’s Effective atomic number (EAN) rule is based on the octet

4 e– pairs by Cl– ions

• One unpaired electron - paramagnetic and attracted by magnets

[Fe(CN)6]3- Fe: (3d64s2)