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to
for
methane in lieu of the tetravalency of
carbon, because it has only two half
filled orbitals available for bond
formation [This explains the bonding in
CO ]. Adding energy to the system
promotes a 2s electron to a 2p orbital,
However, these bonds would not all be of the same length because, s orbitals are closer to the
nucleus, and therefore a bond formed by the overlap of two s orbitals or that between a s orbital
and a p orbital, would be shorter than that formed by the head-on overlap of two p orbitals. The
order of lengths for head on overlap of two orbitals would be as follows:
s-s < s-p < p-p < s-d < p-d < d-d
- Bond length increases
In other words, atomic s orbitals are more deepseated in the atom than atomic p orbitals.
To achieve equal bond lengths, all the orbitals would have to be of the same type. The creation of
identical orbitals occurs by a process of hybridization. Hybridization is an internal linear
combination of atomic orbitals (LCAO), in which the wave functions of the atomic s and p orbitals
are added together to generate new hybrid wave functions.
[Here we will digress from our story a little, to get a greater degree of insight into the history of the
development of atomic structure, which is crucial to our understanding of organic chemistry.]
Q. What is a wave function?
A: Let us keep this question on hold for some time. We will answer it shortly, but we have some
ground to cover before we reach this territory. Before we answer this question, we need to answer
some auxiliary questions:
a) What do we mean by saying that An electron has dual nature?
Ans.: The years post 1900 were momentous, if not uniquely so, only because the roots of the surge
in development of chemical theory were laid in the latter half of the 19 th century, i.e. post 1850.
Workers such as Pasteur, Kekule, Vant Hoff, le Bel, Heitler and London, Lewis, Coulson, Condon, et
al., unearthed fundamentally important stepping stones in particle physics and chemical bonding. The
understanding of the structure of the atom came from twofold approaches both from physics and from
chemistry. Albert Einstein, Compton, Max Planck, Werner Heisenberg, Erwin Schrdinger, Linus
Pauling, Louis de Broglie and other workers performed path-breaking experiments and deductions
that led into radical changes in quantum mechanics and the understanding of the atom.
In short, the particle nature of electrons had already been established by the fact that
electrons exhibited the excitation characteristics typical of particles on absorption of energy, i.e.,
much as molecules of a solid or a liquid or a gas behave more excitedly on receiving energy (which is
the crux of thermal expansion), so too, electrons are also found to be excited along similar patterns
[of course, the presence of the nucleus behind the electron as a charged body=source of
potential=field generator makes all the difference, giving a greater degree of order or restraint to
electronic excitation; an excited electron is still an electron, a negatively charged particle, bound to be
fatally attracted to the nucleus]
Now however, electrons were found to exhibit the particulate characteristics typical of
the results of the photoelectric experiment, and the wave characteristics of Comptons scattering
experiment. Further, known characteristics of waves such as interference, diffraction and polarization,
were found to be innate properties of a beam of electrons. These results and more led Louis de
Broglie to conclude that if energy could have particulate characteristics, then particles might have
wave nature as well. He postulated the existence of what we now know as de Broglie matter waves.
excellent example of a wave function is (x,t). We will encounter this particular wave function almost
everywhere, and especially with the Schrdinger Equation. An orbital is an acceptable solution of
the Schrodinger Equation for the wave function that describes that orbital.
[The story of hybridization resumes at this point]
When four unhybridized atomic orbitals are added together and thoroughly mixed, four hybrid atomic
orbitals are formed. For the carbon atom in the excited state, we have, in the unhybridized state, a
half-filled 2s orbital and three half-filled 2p orbitals. Obviously, by virtue of differences in energy,
extent of overlap and thus bonding efficiency, these unhybridized orbitals cannot bond with the singly
occupied 1s orbitals of each of the four H atoms that expectantly await carbons decision to bond.
Therefore, a hybridization event is inevitable. And so it occurs. An imaginary energy crucible appears,
and we perform the thought experiment of taking the 2s orbital and the three 2p orbitals of carbon and
grinding them into an indiscernible, homogeneous mixture, which we then separate into four identical,
degenerate, hybrid atomic orbitals. Each of these hybrid orbitals has one part s character and three
parts p character(since one s orbital, and three p orbitals have gone into making them) and is
therefore, called a sp3 hybrid atomic orbital.
Thus we have our molecule of methane CH4, with four CH single bonds ( bonds, because they
have cylindrical symmetry*) that are equal in length, energy and spatial distribution. [As a matter of
fact, the methane molecule is perfectly tetrahedral, to the point where it is used as a model for
tetrahedral symmetry (later, much later, when we come across adamantine derivatives, we shall see
what this means).]
In the hybridization process, all bond lengths become equal. The equality of all the HCH bond
angles can be explained by the physical understanding that the bonds in question are basically pairs
of electrons; electrons being like-charged (negatively, to the amount of Q e = 1.6025 x 10-19 C), will
repel each other; repulsion increases the potential energy of the system* and in an attempt to
minimize the energy of the system(the molecule), the electron-pairs(the bonds) will assume the
greatest degree of separation possible in the three dimensional space surrounding the carbon atom.
A simple calculation of solid angles reveals that this angular separation is greatest at the tetrahedral
angle, 109 28. This postulate of electron-pair repulsion forms the cornerstone of the valenceshell
electronpair repulsion theory (VSEPR theory*). According to this theory, electron pairs repel each
other; therefore, the electron pairs that are in bonds or in lone pairs in orbitals around an atom
generally separate from each other as much as possible. Thus, for methane, with four CH single
bonds around a single carbon atom, the maximum angle to which the bonds can separate, to
minimize bond pair-bond pair repulsion is the tetrahedral angle, which is 10928, or approximately
110.
In a similar fashion, the atomic orbitals of carbon can hybridize to form sp2 hybrid orbitals.
Q: How so?
A: Ethene (earlier known as ethylene) has a molecular formula C 2H4. It has a single degree of
unsaturation [expressed in terms of IHD{Index of Hydrogen Deficiency} or DBE{Double Bond
Equivalent}; they indicate the same result, i.e. the number of double bonds in a molecule, though
they are evaluated using different methods.*]
Let us recall the electronic configuration for carbon in its excited state.
In case of ethene, each carbon atom is faced with
Electronic configuration plays an enormously important role in three substituentsH, H and C. In this case, the
hybridization decisions taken by the carbon atom, and indeed atomic orbitals that undergo linear combination
by all atoms. And this in turn, depends on the energy of the
are one s and two p orbitals. This combination
system.
leads to the generation of three equivalent sp 2
hybrid orbitals. The third p orbital remains an
unhybridized atomic orbital. The p-orbital
remains perpendicular to the three sp2 hybrid
orbitals, because, in the process of hybridization,
a plane has been selected. The third p orbital is
perpendicular to this plane.
; GSEC=1s
2s2 2p2
Post-hybridization electronic
configuration of carbon: 1s2
2sp2(3) 2p1
1s2
2sp22sp22sp2 2p1
Therefore we see three bonds formed: two CH bonds formed by the overlap of two of the three
sp2 orbitals from carbon with the two 1s orbitals from the two hydrogen atoms. The third sigma bond,
formed by head-on overlap of the third sp 2 orbital from both the carbon atoms, represents a sp 2-sp2
overlap.
These unbounded p-orbitals then
interact laterally (side-by-side) to form a
bond that is weaker than the sigma
bond and has a different kind of
symmetry, the symmetry; hence
these bonds are also called bonds.
Because the three hybrid orbitals lie in
one plane, the VSEPR theory predicts
that the orbitals are separated by 120
angles. The unhybridized atomic p
orbital lies at a 90 angle to the plane.
This configuration allows for the
maximum separation of all orbitals.
A Telegraph article by Ruchir Joshi. May 17, 2015 : Cloud covered stars - Bengalis remember their artists only selectively
There is an old house near Lansdowne Market that I often pass. On some days I don't think about this house, I
avoid looking at it. On other days I do look at it and then I'm filled with a certain anger and despair. The man who lived in
the house died over a decade ago and the place has become increasingly dilapidated since then; but this is a common
story in this city and hardly a reason for any dramatic feelings. The reason I feel the spike of fury is because the
disintegration of the house reminds me of the shockingly quick fraying of the great, innovative work its occupant produced
and also of the principles by which he did his work.
ones are dealt to us after we are gone. There is a long list of writers or artists who rule with such pomp during their lives
only to have their value shredded by a later time wearing very different critic's spectacles. On the other hand, there is the
example of someone like Vincent Van Gogh, a man who struggled at so many levels thoughout his life and who could not
have possibly imagined the 'brand' he would become, or the obscene amounts his canvasses would one day fetch. Then
there are artists who, without any hubris, know that their place in history is assured, that their work will be recognized and
savoured by generations to come. Then there are ones who would desperately like this to happen but just know that it
won't. And then again there are the ones who genuinely don't care, who don't give a damn what happens to their work or
their name after their passing. In Calcutta's short history we have examples of all of the above, plus some other types.
In the field of cinema, if you'd asked someone, anyone, during the 1980s, whose work would most likely survive
deep into the future, the simple answer would have been 'Satyajit Ray'. If you'd asked the opposite question, as to whose
work would shortly be scattered into the winds of obscurity, there would have been quite a few contenders, but the leading
one would have been Ritwik Ghatak. That Ray's was one of the most major contributions to serious Bengali and Indian
cinema was never in doubt. That Ghatak's films, far fewer in number, (but also great) didn't deserve to mix into dust was
also not being debated. From anyone halfway in touch with the reality of Calcutta's art cinema, the answers would have
been coloured by their knowledge of the two personalities. SR was thorough to the point of OCD mania and there was no
doubt he would leave everything related to his great creative output in meticulously good order. RG, by then already dead,
had been the opposite: immersed in a sea of alcohol, chaotic, mercurial, a brawler at so many different levels, with the
most spectacular graph of self-damage and, consequently, a world champion of self-abnegation, especially in terms of
fripperies
like
posterity.
There were many of us film-makers who loved Ghatak's work, who often found it a stronger source of inspiration
than Ray's films, but, just as we'd had to accept Ghatak's early death, we were also resigned to the early demise of his
original negatives, to the likelihood of the four or five great RG films soon becoming a badly scratched chimerical memory.
Imagine our relief, then, when we heard that Ghatak's main work had been carefully restored in a lab in what was then still
East Berlin. Imagine our joy, at the fag-end of the 1980s, when we saw clean new prints of Subarnarekha or Titash.
When Manikbabu (Ray) died in 1992, not as early as RG, but too early nevertheless, those of us not in his inner circle had
no inkling that the preservation of the SR films was in any kind of jeopardy. We assumed it had all been taken care of,
and, should 1 or 2 of the 10 or 12 most important ones need some repair work there was bound to be a scrum of Western
institutions vying to fund the restoration. A year or so later, I was in London, finishing one of my films in a lab in Soho,
when I heard about the fire in another film lab nearby. Shortly afterwards, we heard that a large part of the Apu trilogy
negatives were burnt in that fire - they had been transiting through London, on their way to being restored in California. It
was the kind of tragic news you put away at the very back of your mind so you can pretend you haven't heard it.
In the mid-1950s, two young Calcutta men, closely helped by a few other people, invented a small new
universe. The taller of the two men was a bit older and the leader of this project (or expedition into the unknown) but the
second man was a founding partner, eventually an almost-equal colleague. The project was, of course, Pather Panchali,
and Ray apparently first asked someone slightly senior to him, Sunil Janah, to do the cinematography for the film, in which
the other novice partner, one Subrata Mitra, would assist. Janah was unwilling to come down from his higher, far more
respectable, calling of photographer to become a mere 'cameraman' for the novice Manik. There was no choice but for
Subrata Mitra to take on the job. Mitra was completely untrained in cinematography; he was 21 when work began on
Pather Panchali, and around 25 when it was finished. Imagine, if you will, two maddeningly obsessive perfectionists,
hugely and relentlessly energetic, driving everyone around them crazy. Imagine, if you can, the lack of experience, the
paucity of resources, the long gaps between the filming schedules, the scraping together of bits of money, keeping the
amateur cast together, the huge battle of the post-production, all managed under the sneering of the great Bangali
yodhhas of Tollygunge and Bombay. With the second film, Aparajito, imagine the now fully confident Mitra, still working
with limited resources, replicating the ricochet of light in Indian interiors by the simple, brilliant, dint of hanging white
bedsheets outside the windows to 'bounce' and corral sunlight. The aesthetics of the immediately previous generations are
all visible in the trilogy, both in Ray's storyboards and Mitra's actual shots, the Tagores and the whole Shantiniketan posse
of Nandalal, Benode Behari and Co., Janah's 1940s socialist black and white documentary ethic, the rawness of the
Italian
neo-realists,
and
yet,
radically
new,
modern
Indian
visual
language
is
being
born.
but
the
question
we
must
ask
ourselves
is
different
one.
The thing is, we in Bengal need both Ray and Ghatak to survive, and Tapan Sinha and Mrinal Sen,
and one-film phenomena like Barin Saha. And whether the Western cinematheques recognize them or not, we also need
to remember and honour the amazing so-called 'technicians', the master-artists who, with the directors, formed the teams
that created our great cinema, the Mitras, the Dilip Mukherjees, the Baby Islams, the K.K. Mahajans, the Bansi
Chandraguptas, the Dulal Duttas. Every time I look at Subrata Mitra's crumbling house on Lansdowne Road I'm reminded
that this city, with all its peacocking intellectual self-regard, has managed just to name the SRFTI and the small road
where he lived after Satyajit Ray and nothing more. For all the Loknayak Metro stations and Uttam Nagars we haven't
named even a photo-booth after Subrata Mitra, we haven't commemorated Ritwik Ghatak with even a chullu kiosk or a
bangla liquor shop.
?