PHOTOCHEMISTRY
CHD 223 – Industrial and Engineering Chemistry
What is Photochemistry?
Photochemistry is the branch of chemistry concerned with the chemical
effects of light.
Generally, this term is used to describe a chemical reaction caused by
absorption of light
Wavelength
• Ultraviolet 100 – 400 nm
• Visible light 400 – 750 nm
• or Infrared radiation 750 – 2500 nm
Some of the common photochemical reaction
• Ionization
• Electron transfer
hϑ
• Dissociation
• Addition
Law of Photochemistry
1st Grothus – Draper Law
According to this law, only those radiations which are absorbed by the
reacting system are effective in producing a chemical change.
2nd Stark- Einstein Law
According to this law, each molecule taking part in chemical reaction
induced by exposure of light absorbs one quantum of radiation, causing
the reaction.
Determine One Einstein
where,
From the 2nd law, we have
Plank constant, h = 6.625 x 10-27 erg
E = 𝑁ℎ𝜗 (1)
Speed of light, c = 3 x 1010 cm/sec
= N ℎ 𝐶/λ (2)
Avogadro number, N = 6.02 x 1023
Substituting in 1, becomes
E = Kcals per mole
We have
E=
Wavelength Energy absorbed per mole, K cal
1. Violet light 4000 Ao 71
2. Red Light 7000 Ao 38
Quantum Efficiency ()
𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠𝑟𝑒𝑎𝑐𝑡𝑖𝑛𝑔𝑖𝑛𝑎𝑔𝑖𝑣𝑒𝑛𝑡𝑖𝑚𝑒
∅=
𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑞𝑢𝑎𝑛𝑡𝑎𝑜𝑓 𝑙𝑖𝑔h𝑡𝑎𝑏𝑠𝑜𝑟𝑏𝑒𝑑𝑖𝑛 𝑡h𝑒𝑠𝑎𝑚𝑒𝑡𝑖𝑚𝑒
Calculate the quantum efficiency for the photochemical reaction,
where 2 x 10-5 moles of Y are formed on absorption of 12 x 10 7 ergs using light of
3600 Ao.
Solution:
Energy associated with one quantum = 10 x 10-12 ergs (since, E = ℎ𝜗 = h )
Number of quanta of radiation absorbed =
= = 1.2 x 1019
Number of molecule reacted = 2 x 10-5 x 6.02 x 1023 = 12.04 x 1018
= =1
Types of photochemical reactions
Direct light induced or non-sensitized reactions
Photosensitized reaction
4/2/2021 9
Direct light induced or Non-sensitized reactions
The molecules absorbs the light undergoes various secondary process to
give the final products of the reactions.
4/2/2021 10
Photosensitized Reaction
Donor (D)
Acceptor (A)
Donor
• Absorb the light
• Becomes excited
• Transfer the excitation energy
Acceptor
• The excited energy from D will be absorbed by A and undergoes the process
Sensitization
4/2/2021 11
4/2/2021 12
Photolysis
Photolysis, chemical process by which molecules are broken down into smaller units through the absorption
of light.
The best-known example of a photolytic process is the experimental technique known as flash photolysis,
employed in the study of short-lived chemical intermediates formed in many photochemical reactions. The
technique, which was developed by the English chemists R.G.W. Norrish and George Porter in 1949, consists
of subjecting a gas or liquid to an intense burst of light lasting a few microseconds or milliseconds, followed
by a second, ordinarily less intense flash. The first flash dissociates the absorbing compound into short-lived
molecular fragments and the second flash provides a means for their identification by spectrophotometry.
The method is a valuable tool for the identification of transient chemical intermediates and hence for the
study of mechanisms of fast chemical reactions.
4/2/2021 13
Apparatus for photochemical studies
𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠 𝑟𝑒𝑎𝑐𝑡𝑖𝑛𝑔 𝑖𝑛𝑎𝑔𝑖𝑣𝑒𝑛 𝑡𝑖𝑚𝑒
∅=
𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑞𝑢𝑎𝑛𝑡𝑎 𝑜𝑓 𝑙𝑖𝑔h𝑡 𝑎𝑏𝑠𝑜𝑟𝑏𝑒𝑑 𝑖𝑛 𝑡h𝑒 𝑠𝑎𝑚𝑒𝑡𝑖𝑚𝑒
Detector
Reaction cell with
Focusing Monochro e.g. chemical
Light source transparent
Lens mator actinometer or
windows
photocell
e.g. Uranyl oxalate actinometer
(0.05 M oxalic acid and 0.01 M
uranyl sulphate in water)
UO2 2+ + hϑ )* [ wavelength 2500 – 4350 Ao]
(UO2 2+)* + COOH + CO2 + CO + H2O*
COOH
Photosynthesis
Photosynthesis takes place in two sequential stages
i. The light-dependent reactions;
ii. The light-independent reactions, or Calvin Cycle.
4/2/2021 16
The light-dependent reactions
Light-dependent reactions require sunlight.
In the light-dependent reactions, energy from sunlight is absorbed by
chlorophyll and converted into stored chemical energy, in the form of
the electron carrier molecule NADPH (nicotinamide adenine
dinucleotide phosphate) and the energy currency molecule ATP
(adenosine triphosphate).
The light-dependent reactions take place in the thylakoid membranes
in the granum (stack of thylakoids), within the chloroplast.
4/2/2021 17
PS II
Photosystem
The process that converts light energy into chemical
energy takes place in a multi-protein complex called a
photosystem. Two types of photosystems are embedded
in the thylakoid membrane: photosystem II ( PSII) and
photosystem I (PSI).
Each photosystem plays a key role in capturing the energy from sunlight by exciting
electrons. These energized electrons are transported by “energy carrier” molecules,
which power the light-independent reactions.
PS I
4/2/2021 18
Photosystems consist of a light-harvesting complex and a reaction center. Pigments in the light-harvesting
complex pass light energy to two special chlorophyll a molecules in the reaction center. The light excites an
electron from the chlorophyll a pair, which passes to the primary electron acceptor. The excited electron
must then be replaced. In photosystem II, the electron comes from the splitting of water, which releases
oxygen as a waste product. In photosystem I, the electron comes from the chloroplast electron transport
chain.
The two photosystems oxidize different sources of the low-energy electron supply, deliver
their energized electrons to different places, and respond to different wavelengths of light.
4/2/2021 19
The light-independent reactions, or Calvin Cycle.
In the light-independent reactions or Calvin cycle, the energized electrons from the light-dependent
reactions provide the energy to form carbohydrates from carbon dioxide molecules. The light-independent
reactions are sometimes called the Calvin cycle because of the cyclical nature of the process.
Although the light-independent reactions do not use light as a reactant (and as a result can take place at
day or night), they require the products of the light-dependent reactions to function. The light-independent
molecules depend on the energy carrier molecules, ATP and NADPH, to drive the construction of new
carbohydrate molecules. After the energy is transferred, the energy carrier molecules return to the light-
dependent reactions to obtain more energized electrons. In addition, several enzymes of the light-
independent reactions are activated by light.
4/2/2021 20
Thank you
