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    Photo Chemistry

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    divya sachdeva
    In depth about photo chemistry

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    © All Rights Reserved

    Photo Chemistry

    Uploaded by

    divya sachdeva
    4 views44 pages
    In depth about photo chemistry

    Copyright

    © © All Rights Reserved

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    In depth about photo chemistry

    Copyright:

    © All Rights Reserved
    4 views44 pages

    Photo Chemistry

    Uploaded by

    divya sachdeva
    In depth about photo chemistry

    Copyright:

    © All Rights Reserved
    of 44

    Photo Chemistry

    Photochemistry studies of those molecules


    which absorbs light radiation of spectrum
    in uv(100-400nm) and visible (400-750nm)
    region and become electronically excited
    Basic laws of Photochemistry
     First law or Grothus-draper law
     2nd law or Stark-Einstein law

    1-The first law states that light must be absorbed for photochemistry to occur
    If a light of particular wavelength is not absorb by the system no photochemistry
    will occur and no changes occur no matter how long one irradiates with the
    wavelength of light.Only that light which is abosorbed by a system can cause
    chemical change
    R R* P
    Second law of photochemistry
    • IT STATES THAT EACH PHOTON OF LIGHT
    ABSORBED BY A CHEMICAL SYSTEM, ONLY
    ONE MOLECULE IS ACTIVATED FOR A
    PHOTOCHEMICAL REACTION OR ONE
    QUANTUM OF LIGHT IS ABSORBING AND
    REACTING SUBSTANCE THE DISAPPEARS
    INTRACTION OF
    ELECTROMAGNETIC
    RADIATION WITH
    MATTER
    Photochemsitry is the study of reactions
    which are caused by intraction of light
    Here light means spectrum When beam
    of sunlight pass though a prism it splits
    into seven different colours this set of
    colours obtained by spliting is called
    Spectrum
    THE ELECTROMAGNETIC
    SPECTRUM
    The electromagnetic spectrum represents the range of energy
    from low energy, low frequency radio waves with long
    wavelengths up to high energy, high frequency gamma
    waves with small wavelengths.
    The intraction of electromagnetic radiation with matter, first
    we should understand the complete spectrum of
    electromagnetic radiation from radioactive rays to radio
    waves Cosmic rays come from the and are known to be
    radiation of highest energy radio waves have the longest
    wavelenght more than 10-7nm
    Properties of
    electromagnetic waves

    1- All matter contation charged particle that are always


    moving therefore all object emit electromagnetic waves

    2- The wavelength becomes shorter all the temperature


    of matter increases

    3- EM waves carry radiant energy


    Parameters of
    electromagnetic waves

    WAVELENGTH- distance from


    crust to crust

    FREQUENCY- Number of
    wavelength that pass a given
    point in 1 second

    WAVENUMBER- It is the
    number of waves per unit cm
    For photochemistry only
    UV and visible a small
    part of the full
    electromagnetic
    spectrum is needed
    Classification of
    Electronic Transitions
    • The wavelength of an electronic
    transition depends on the
    energy difference between the
    G.S. and the E.S. It is a useful
    approximation to consider the λ
    of to be determined by the ΔE of
    MO originally occupied by the
    e’s at G.S. and the higher
    excited MO in E.S.
    • The order: σ ->π ->n->π* ->σ*
    Different type of
    UV transitions
    transition
    • 1.Σ→Σ* TRANSITIONS: FOR CPDS.

    type
    WITH ΣBOND ONLY, HIGH ΔE, SHORT Λ
    (< 200 NM).
    • APPEARS IN SATD. HYDROCARBONS
    WITH Σ ORBITAL AND TRANSITION TO
    ANTIBONDING Σ* OR TO MOLECULAR
    RYDBERG ORBITAL (HIGHER VALENCE
    SHELL ORBITALS, 3S, 3P, 4S, …), AND
    INVOLVES LARGE ΔE, AND SMALL ΛMAX
    THAT APPEARS IN FAR-UV REGION.
    • EX. CYCLOPROPANE ΛMAX 190 NM.
    •
    transition
    type
    • 2. n→π* transitions : the
    excitation of an electron on an
    nonbonding orbital, such as
    unshared pair e’s on O, N,
    S,..to an antibonding π*,
    usually in an double bond with
    hetero atoms, such as C=O,
    C=S, N=O, etc. A sym.
    forbidden and low intensity
    transition.
    UV
    transition
    type
    • 3.π→π* transitions : for cpds.
    containing double, triple bonds, or
    aromatic rings; a π electron is excited to
    an antibonding π* orbital. This is
    usually a sym. allowed and high
    intensity transition.
    • Ethylene : absorbs at 162 nm (10000),
    in vacuum UV. Extended conjugation
    lowers, ΔE, and increase in λmax, if
    extended beyond 5 double bonds then
    getting into visible region.
    UV transition
    type
    • 4. n→σ* transitions: excitation from
    nonbonding orbital to an antibonding
    σ* orbital.
    Ex. CH3OH(vap.) 183 nm (ε 150)
    NEt3(vap.) 227 nm (900)
    MeI(hexane) 258 nm (380)
    • 5. Rydberg transition: mainly to higher
    excited states. For most organic
    molecules occurs at λ below 200 nm.
    Part of a series of molecular electronic
    transitions occurs with narrowing
    spacing nearing the ionization
    potential of organic molecule.
    Carbonyl chromophore of
    3-methylcyclohexanone
    Orbital Spin and
    states
    • Diagram showing the ground state and
    excited state configuration of
    carbonyl chromophore.
    • Singlet state (S) have electron spin
    paired and triplet state (T) have two
    spins parallel.
    • n orbital containing two electrons is
    perpendicular to πorπ* orbitals.
    • Subscript 0 refers to G.S., 1 to 1 st.
    E.S., 2 to 2 nd. E.S.
    Transition shown by
    different types of
    molecules
    Jablonski
    Diagram
    SOME TERMS USED IN JABLONKI DIAGRAM

    !- FLUORESCENCE- WHEN A LIGHT RADIATION


    IS ABSORBED BY A COMPOUND ITS
    ELECTRON GOES TO HIGHER ENERGY LEVEL
    FROM LOWER ENERGY LEVEL. WHEN THE
    ELECTRON RETURNS TO THE NORMAL
    POSITION WITH THE EMOTION OF LIGHT
    ENERGY
    IT TAKES PLACE AS SOON AS THE LIGHT IS
    ABSORBED AND CASES AS SOON AS LIGHT IS
    STOPPED
    THE TIME PERIOD TAKEN BY THIS PROCESS IS
    10-8 SEC
    Phosphorescence-: The molecule with relatively stable
    excited state may undergo transition to a meta stable singlet or
    triplet state and after some time return to the gram state by
    emission of UV or visible vision
    It is also known as slow fluorescence
    The time taken by this process is 10-3 second

    Internal conversion(IC)- a Molecule returns to its ground state s0 from


    its exited singlet state s1 or s2 by giving up its energy as heat.

    Intersystem crossing(Isc) - Some


    molecules from the s1 state may
    drop to triplet state t1 state thus the
    transition from exited singlet to
    exited triplet state

    S0- singlet ground state


    S1 and S2 exited singlet singlet state t1
    triplet state
    OVERALL JABLONSKI ENERGY
    DIAGRAM
    FRANK CODON
    PRINCIPLE
     Given by James frank in 1925
     It states that as electron move very faster than nuclei as effectively stationary during an
    electronic transition
     This principle allow to calculate the probability of a transition from some vibrational level
    V1 of initial state to another vibrational level of the final state

    Frank codon potential energy diagram

    The potential wells are shown favouring


    transition between v=0 to and V=2
     Frank codon principle is a rule in spectroscopy and quantum chemistry that explain the
    intensity of vibronic transition

    Vibronic transition are the simultaneous change in electronic and vibrational energy level of
    a molecule due to absorption or emission of a photon of the energy level

    According to GOVINJEE – What happen to atom absorbes a photon when light is absorbed
    each quantum is taken up by a single atom The absorbing atom or molecule is thus exited that
    is lifted from its normal state of lowest energy (highest stablity ) to exited state (energy rich
    state)

    According to Niel Bohr’s theory of atomic and molecular structure an ato or molecule can
    exits only in a series of discreet state of electronic energy
    APPLICATIONS OF PHOTOCHEMISTRY

     Fluorescent light tubes

     Luminiscent dials for watches

     X ray TV screen

     Paints in advertisement hordings which show more brilliance by utilising fluresence

    Optical brightness in white dress materials

    Detection of cracks in metal works etc

    In flash photolysis

    In laser technique


    FLASH
    PHOTOLYSIS
    Given by Manfred eigen, ronald, george porter
    These were awarded nobel prize in 1967 in chemistry
    flash photolysis is used extensively to study reaction
    that happen extremely quickly even in femento second or
    pico second

    It is used to take pictures of fast moving planes, rockets


    and missiles

    It is used by researchers to study light induced process


    in organic molecules, polymers nano particles,
    semiconductors, photosynthesis in plants
    Photo
    chemical
    Those chemical reaction which takes place in
    the presence of light is known as
    photochemical reaction

    reaction
    Types of photochemical reaction
    1- Photo Reduction
    2- Photo addition
    3- Photo isomerisation
    4-Photo oxidation
    5- Photo dissociation
    Photo Reduction Reaction
    Reduction takes place in the presence of UV or visible light is known as Photo Reduction
    Reaction

    Overall Reaction
    Mechanism of this Reaction
    1- Initiation- formation of radical- breathing of CO bond the light is needed in this reaction to
    break the pi- bond between the Co in the Co group of benzophenone forming a di radical
    2- Formation of benzyhydrol radical

    Benzohydrol (radical) Initiation(first)


    3- Formation of
    benzyhydrodiradical
    and
    THE NEWLY Acetone
    FORMED RADICAL IS NOW HIGHLY REACTIVE
    ENABLING IT TO OFFER A HYDROGEN ATOM TO THE OXYGEN OF
    ANOTHER BENZOPHENONRADICAL THAT RESULTING IN THE
    FORMATION OF STABLE MOLECULE ACETONE AS WELL AS
    ANOTHER BENZOHYDROLRADICAL
    Photooxidation
    Reaction
    Those oxidation
    reaction which
    takes place in the
    presence of visible
    light
    Photodissotiation
    Reaction
    Those photo chemical
    dissociation reaction
    which takes place in the
    presence of light is
    known as photo
    dissociation reaction
    Photochemical cycloaddition reaction
    Those cycloaddition reaction which takes place in the presence of light
    PHOTOCHEMISTRY OF
    CARBONYL COMPOUND
    To study the photochemiacal reaction of carbonyl compouds
    there are found four important primary photochemical
    reactions-
    1-In a photochemical reaction, when cleavage of alpha-bond to
    carbonyl group takes place it is called alpha cleavage or norrish
    type-1 process
    2- If a beta bond to the carbonyl group has to cleaved during a
    photochemical reaction it will acccompany an abstraction of
    intramolecular hydrogen bond this is called nourish type-2
    process
    3- if the reaction is intermolecular the hydrogern atom will
    abstract from the oxygen of the carbonyl group
    4- Addition of carbonyl oxygen will occur to a carbon-carbon
    double bond
    Norrish type-1 Process-: In nourish type-1
    process cleavage takes in alpha carbon bond In
    the the initial primary process a diratical is
    formed by photolysis of cyclohexanone and
    then it is followed by secondary process which
    results in the formation of a mixture of carbon
    mono-oxide cyclopentane and 5-hexanal
    Norrish type 2nd process-: Norrish type 2nd process
    or cleavage is also known as beta cleavage this
    type of reaction is possible if bond between alpha
    and beta carbon is weak

    In open chain compound


    Mechanism-
    Intra molecular photo recations in beta, gamma unsaturated carbonyl compound- In these
    reaction carbonyl compouds consist of alpha cleavage the oral reaction follow by two
    modes
    1- In the first 1,3-acyl shift is involved which form an isomeric beta gamma unsaturated
    ketones
    2- In this step ring closure process takes place
    Reaction of carbonyl compound with alkyne

    In this reaction onetime is formed which gets


    isomerism and gave alpha beta unsaturated
    carbonyl compounds this reaction undergo
    photochemical reaction

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