General Chemistry (CHEM F111)

Lecture-21
05/03/2024
Recap
*Gibbs free energy (Description of spontaneity of
a process with the property of system alone)

*Phase equilibrium of pure substances: Variation

of G with T and P: How phase transitions depend
on T and P?

*Reaction at equilibrium: Thermodynamic

background, variation of Gibbs energy of a
reaction mixture with composition, Standard
reaction Gibbs Energy
Today’s Topic

* Standard reaction Gibbs Energy, Standard Gibbs

energy of formation

*Chemical Kinetics-
Reaction Mechanism
Steady State approximation
 Equilibrium
At equilibrium, rG = 0, or
rG = − RT ln Qeq = − RT {(aCc aDd)/(aAa aBb)}eq
rG = − RT ln K
At equilibrium, Q = K

Generally speaking,
Reaction feasible if rG << 0, ie., K >> 1
and not so if rG >> 0, ie., K << 1
Of course, it is rG which will ultimately decide the
feasibility, with rG = RT ln(Q/K)
 Equilibrium Composition
If K  1 (typically K 103),
corresponding rG  -17kJ/mol
Reaction has tendency to form products at equilibrium

If K  1 (typically K 10-3),
corresponding rG  +17kJ/mol
Reaction has largely unchanged reactants at equilibrium

If K is comparable to 1 (typically 103 to

10-3 ), both reactant and products will be
formed at equilibrium
 Criteria of Spontaneity
Since rG = rH − T rS
(a) If rH < 0 (exothermic) and rS > 0
then rG < 0 at all T
(b) If rH < 0 (exothermic) and rS < 0
then rG < 0 for T < rH / rS
(c) If rH > 0 (endothermic) and rS > 0
then rG < 0 for T > rH / rS
(d) If rH > 0 (endothermic) and rS < 0
then rG  0 at all T, and therefore the process is non-
spontaneous.
Variation of rG for an
endothermic reaction
(rH > 0) with rS > 0
 Standard Reaction Gibbs Energy

rG =
iGi,m(products) − iGi,m (reactants)
However the absolute Gibbs energies are not
known. One can find from the following eqn.:

rG = rH −T rS 

With rH from formation enthalpies and

rS from absolute entropies.
 Standard Gibbs Energy of Formation

The Standard Gibbs Energy of Formation

fG of a substance is defined as the
Standard Gibbs Energy of the reaction
leading to the formation of one mole of the
substance from its elements in their reference
states, ie., the element in its most stable state
under the prevailing conditions.
Formation Reactions
H2(g) + ½ O2(g) → H2O(l) fG 298 (H2O(l)) =
− 237 kJ/mole
C(s,graphite) + O2(g) → CO2(g) fG298(CO2(g))
= − 394.4 kJ/mole
C(s,graphite) → C(s,diamond)
fG298(C(s,diamond)) = 2.9 kJ/mole
½ H2(g) + ½ Br2(l) → HBr(g) fG298(HBr(g)) =
− 53.4 kJ/mole
Standard Gibbs Energy of Formation

Endergonic

Exergonic
Chemical
Kinetics
 Kinetics versus Thermodynamics

Thermodynamics tells us which direction a

reaction will go (e.g. at room temperature and
standard pressure, carbon is stable in a form of
graphite)

Kinetics can tell us how quickly it will get

there (e.g. A diamond will not convert to
graphite during your lifetime)
 Chemical Kinetics
• The study of reaction rates
– How fast does a reaction proceeds and what
factors affecting it
– A measure of the change of the
concentration of a reactant (or a product) as
a function of time
The study of rate yields information on
the mechanism by which a reaction
occurs at molecular level.
 Reaction Rate
Consider the reaction N2(g) + 3H2(g) → 2NH3(g)
Rate = −d[N2]/dt = −1/3 d[H2]/dt = ½ d[NH3]/dt
For example, if at a given time rate of formation of
NH3 is 1.2 mmol L-1 s-1, then rate of consumption of
N2 is 0.6 mmol L-1s-1.
For the general reaction n1A+n2B → n3C+n4D
Rate = −1/n1 d[A]/dt = −1/n2 d[B]/dt = 1/n3 d[C]/dt =
1/n4 d[D]/dt
 Suppose a chemical reaction is represented as,
n1A+n2B → n3C+n4D

The rate of the chemical reaction:

The numerical magnitudes of x and y will come

from experimental determinations and have no
bearing on n1 and n2

(x+y) total ‘order’ of the reaction

(n1+n2) ‘molecularity’ of the reaction
 Determination of an order of a reaction

• Graphical method or method of integration

• Differential method or method of initial rate

• Method of half reaction time

• Method of isolation or Ostwald method

 Integrated rate laws

Order Reaction type Rate law Integrated rate law

0 A→P rate = k [P] = kt for kt  [A]0
1 A→P rate = k[A] [P] = [A]0(1 − e−kt)
kt[A]02
2 A→P rate = k[A] 2
[P] =
1 + kt[A]0

[A]0 [B]0 (1− e([B]0 − [ A ]0 )kt )

A+B→P rate = k[A][B] [P] =
[A]0 − [B]0 e([B]0 − [ A ]0 )kt
 Temperature Dependence
Rates of most reactions increase with increasing T
Plot of ln k versus 1/T predicted to be linear with
slope equal to – Ea/R

Arrhenius Equation: k = A e−Ea/RT

Arrhenius parameters: A – pre-exponential factor,
and Ea – Activation Energy.
Generally observed for reactions both in the gas
phase as well as liquid phase reactions.
 Reaction Mechanisms
• Reactions may occur all at once or
through several discrete steps.
• Each of these processes is known as an
elementary reaction or elementary
process.
The sequence of events that describes the
actual process by which reactants become
products is called the ‘reaction mechanism’.
Deducing Mechanisms From Rate Data
 Example of Complex reactions
(combinations of elementary steps)
K
1
A B Reversible unimolecular
K-1

K
1 B
A Parallel unimolecular
K2
C
K K2
1 Consecutive unimolecular
A B C
K
1 K2
A B C Consecutive reversible
K-1
unimolecular
 Elementary Reactions
(Characterized by molecularity)

Unimolecular Bimolecular
 Elementary Processes

• Intermediates are produced in one

elementary process and consumed in
another.
• One elementary step is usually slower than
all the others and is known as the rate
determining step.
 Multistep Mechanisms
• In a multistep process, one of the steps will be
slower than all others.
• The overall reaction cannot occur faster than this
slowest, rate-determining step.
 Rate Laws and Rate Determining Steps
Writing plausible reaction mechanisms:
• The sum of the elementary steps must give the
overall balanced equation for the reaction.
• The rate-determining step should predict the same
rate law that is determined experimentally.
The rate-determining step is the slowest step in
the sequence of steps leading to product
formation.
 Example 1: Slow Initial Step
NO2 (g) + CO (g) ⎯⎯→ NO (g) + CO2 (g)

• The rate law for this reaction is found

experimentally to be
Rate = k [NO2]2
• CO is necessary for this reaction to occur, but the
rate of the reaction does not depend on its
concentration.
• This suggests the reaction occurs in two steps.
 Slow Initial Step
• A proposed mechanism for this reaction is
Step 1: NO2 + NO2 ⎯⎯→ NO3 + NO (slow)
Step 2: NO3 + CO ⎯⎯→ NO2 + CO2 (fast)
• The NO3 intermediate is consumed in the second step.
• As CO is not involved in the slow, rate-determining
step, it does not appear in the rate law.
 Example 2: Fast Initial Step

2 NO (g) + Br2 (g) ⎯⎯→ 2 NOBr (g)

• The rate law for this reaction is found

(experimentally) to be
Rate = k [NO]2 [Br2]
• Because termolecular processes are rare, this
rate law also suggests a two-step mechanism.
• A proposed mechanism is
• Step 1: NO + Br2 ⇄ NOBr2 (fast)
rate constants: k1 and k-1
• Step 2: NOBr2 + NO ⎯⎯→ 2NOBr (slow)
rate constant: k2

• The rate of the overall reaction depends upon the

rate of the slow step.
• The rate law for that step would be
Rate = k2[NOBr2][NO]
• But how can we find [NOBr2]?
 Steady State Approximation
“Concentration of intermediate species, here
NOBr2, remains small and almost constant
throughout reaction”.

d[NOBr2]/dt = 0 = k1[NO][Br2] - k-1[NOBr2] –

k2[NOBr2][NO]
[NOBr2] = k1[NO][Br2] /(k-1+k2[NO])
Rate of formation of NOBr =

k1 k2[NO]2[Br2]/(k-1+k2[NO])
Rate of formation of NOBr = k1 k2[NO]2[Br2]/(k-1+k2[NO])

When the rate of decomposition of NOBr2 is much greater

than the rate of its reaction with NO, ie., k-1 [NOBr2] >>
k2[NOBr2][NO]
Rate of formation of NOBr = k1k2[NO]2[Br2]/k-1 ≈
k[NO]2[Br2]

If k-1 [NOBr2] << k2[NOBr2][NO] (for example)

Rate of formation of NOBr = k1[NO][Br2]

Slowest step is rate determining

Slowest step is rate determining
The reaction profile: first step is rate
determining
 Spectroscopy
Spectroscopy is a general term referring to the interactions of various
types of electromagnetic radiation with matter.

Electric and magnetic field

components
of plane polarized light

Exactly how the radiation interacts with matter is directly dependent on

the energy of the radiation.
Electromagnetic Radiation
 What is a spectrum/spectra ?
➢ The response of the atoms, molecules, nuclei etc.,
when you shine electromagnetic radiation on
them.
➢ We can measure transmittance, absorption,
scattering etc., depending on nature of the
interaction
How does a spectra look? Y axis value (response) depends
on the experiment
 Different Spectroscopic techniques
Spectroscopy
The higher energy ultraviolet and visible
wavelengths affect the energy levels of the
outer electrons.

Infrared radiation is absorbed by matter

resulting in vibration of molecules.

Radio waves are used in nuclear magnetic

Resonance and affect the spin of nuclei in a
magnetic field.
The energy states are said to be quantised
because a photon of precise energy and
frequency (or wavelength) must be absorbed
to excite an electron or molecule from the
ground state to a particular excited state.

Since molecules have a unique set of energy

states that depend on their structure, IR, UV-
visible and NMR spectroscopy will provide
valuable information about the structure of the
molecule.
Electronic Spectroscopy
 Electronic Transitions
Occur in the visible (400 to 700 nm) and ultraviolet
(200 to 400 nm) regions of spectrum.
Responsible for the color of many objects and
many photochemical reactions.

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Visible absorption spectrum of chlorophyll

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 Absorption spectroscopy is the study of
electromagnetic radiation absorbed by atoms or
molecules that change energy levels.

• Specific chemical compounds have a specific

absorption spectrum that acts as a fingerprint.

• Moreover, the amount of absorption is related to

the amount of absorbing compound.

• Absorption spectroscopy can be used to

determine the concentration of chemical
compounds in samples 43
 Beer-Lambert law
•Transmittance T of a given sample, at a given
frequency, T = I/I0, where I and I0 are the
transmitted and incident intensities respectively.
•Absorbance A = log I0/I = -log T
•Beer-Lambert law: A =  J l where l is the
sample length (path length), [J] is the molar
concentration of the absorbing species, and  is
called the molar absorption coefficient with
dimensions of 1/(concentration)(length).
•Intensity transmitted decreases exponentially 44with
path length.
 Absorption Spectrum of a Mixture

A2 Self Study
A1
Absorbance, A →

εB1[B]L
εA2[A]L

εB2[B]L
εA1[A]L

Wavelength, λ →

Joint absorption region45

 Determining concentrations in a mixture:
A = AA + AB = (εA[A] + εB[B])L
A1 = (εA1[A] + εB1[B])L and A2 = (εA2[A] + εB2[B])L
Self Study
➢Multiply A1 by εB2 and A2 by εB1
εB2 A1 = (εB2 εA1[A] + εB2 εB1[B])L and
εB1 A2 = (εB1 εA2[A] + εB1 εB2[B])L
εB2 A1 - εB1 A2 = (εB2 εA1 - εB1 εA2)[A]L

➢Multiply A1 by εA2 and A2 by εA1

εA2 A1 = (εA2 εA1[A] + εA2 εB1[B])L
εA1 A2 = (εA1 εA2[A] + εA1 εB2[B])L
εA1 A2 - εA2 A1 = (εA1 εB2 - εA2 εB1)[B]L

[A] = (εB2 A1 - εB1 A2) / (εB2 εA1 - εB1 εA2)L

[B] = (εA1 A2 - εA2 A1) / (εA1 εB2 - εA2 εB1)L
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Two inter-related absorbing species
Quantitative
analysis
Great for non-
aqueous
titrations

Isosbestic points
Single clear point, can exclude
intermediate state, exclude
light scattering and Beer’s law
applies

Binding of a lanthanide complex to

an oligonucleotide
Electronic absorption spectrum often very broad,
particularly in solution.
Vibronic Transitions
Many bands may merge to give a single broad band with
unresolved vibrational structure.

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