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Chapter 4 Photochemistry

This document summarizes key concepts in photochemistry. It discusses: 1) The basic concepts of photochemical processes including primary photon absorption, primary and secondary photochemical stages, and the laws of photochemistry. 2) Kinetic concepts including determining the lifetime of excited states, mechanisms of decay of excited singlet states, and fluorescence quantum yield and lifetime. 3) Examples of photochemical reactions and calculations involving photon energy, quantum yield, and photosynthetic reactions.

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Hien Hoang
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31 views

Chapter 4 Photochemistry

This document summarizes key concepts in photochemistry. It discusses: 1) The basic concepts of photochemical processes including primary photon absorption, primary and secondary photochemical stages, and the laws of photochemistry. 2) Kinetic concepts including determining the lifetime of excited states, mechanisms of decay of excited singlet states, and fluorescence quantum yield and lifetime. 3) Examples of photochemical reactions and calculations involving photon energy, quantum yield, and photosynthetic reactions.

Uploaded by

Hien Hoang
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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Chapter 4

PHOTOCHEMISTRY

1. THE BASIC CONCEPTS

2. KINETIC OF PHOTOCHEMICAL PROCESSES


THE BASIC CONCEPTS 1

1.1 PHOTOCHEMICAL PROCESSES

 Primary photon absorption: molecules or


atoms absorb energy of photon to
promote electron to higher energy orbital

 Primary photochemical stage: excited


molecules or atoms participate in
reactions

 Secondary photochemical stage: products


of the primary stage react with the
remaining reactants
THE BASIC CONCEPTS 2

1.2 LAWS OF PHOTOCHEMISTRY


 Grotthuss – Draper (first law of photochemistry): only the light
which is absorbed by a molecule can be effective in producing
photochemical changes in the molecule
 Einstein (second law of photochemistry): each molecule taking
part in a reaction induced by exposure to radiant energy absorbs
one quantum of radiation causing the reaction. It should be
emphasized that this applies only to the primary process of light
absorption
 The energy absorbed by one mole of the reacting molecules:

𝑨 𝑨

E is called one Einstein ; 1 Einstein = 1 mol photon = NA.photon


THE BASIC CONCEPTS 3

1.2. LAWS OF PHOTOCHEMISTRY


 Kasha: when absorbing a photon, the molecule has a certain probability of being excited to the excited
singlet state (S) or excited triplet state (T).
THE BASIC CONCEPTS 4

1.2. LAWS OF PHOTOCHEMISTRY


 Beer – Lambert:
Io (ec/cm2.s): the intensity
monochromatic light
IT: the intensity of the
light reduces
IZ: the light entering the
infinitesimal block
THE BASIC CONCEPTS 5

 The fraction of light absorbed would therefore be = dI/Iz = – σ × N × dz


(The negative sign is placed to indicate absorption of light.)

 Integral of this infinitesimal block for the whole sample (from z = 0 to z = b)


ln IT – ln I0 = – σ × N × b – ln ( IT / I0) = σ × N × b
– ln ( IT / I0) = (6.023 × 10 23) × C / 1000 × σ × b (C is the concentration in moles/litre)

log ( IT / I0) = [(6.023 × 10 20 × σ )/ 2.303] × C × b

log ( IT / I0) = ɛ × C × b
THE BASIC CONCEPTS 6

1.3. QUANTUM YIELD


 Quantum yield, , is the ratio of the number of molecules reacted (δN) to the number of photons
absorbed (δNo)
∆𝐍 Number of molecules reacted
𝛟= =
∆𝐍𝐨 Number of photon absorbed

𝒓𝒂𝒕𝒆 𝒐𝒇 𝒑𝒓𝒐𝒄𝒆𝒔𝒔 𝒗
(*)
𝒊𝒏𝒕𝒆𝒏𝒔𝒊𝒕𝒚 𝒐𝒇 𝒍𝒊𝒈𝒉𝒕 𝒂𝒃𝒔𝒐𝒓𝒃𝒆𝒅 𝑰𝒂𝒃𝒔

∆I: absorbed radiant energy


E = hν: photon energy

 To excite 1 mole of substance, 6.02×1023 photons are required to be absorbed. (No photon # 1 Faraday)
 Ví dụ 1: xét phản ứng sau: 2HI H2 + I2 ở vùng bước sóng λ = 280 – 300 nm, phản ứng xảy
ra theo sơ đồ sau:
 Ví dụ 2: xét phản ứng sau: 2NO2 NO + O2 ở vùng bước sóng λ = 366 nm, phản ứng xảy ra
theo sơ đồ sau:
 Ví dụ 3: xét phản ứng sau

C6H5CH=CHCOOH + Br2 C6H5CHBr-CHBrCOOH

Phản ứng xảy ra ở bước sóng λ = 435,8 nm và 30 oC. Khi chiếu sáng với cường độ 1,4×10-3 J/s
trong thời gian 1105 giây thì lượng brom giảm 0,075 mmol. Tính hiệu suất lượng tử , cho
biết 80% ánh sáng đi qua dung dịch bị hấp thụ

(SV tự giải)
 Ví dụ 4: một dung dịch gồm acid oxalic 0,01 M và ion uranyl sulfat (UO22+) 0,05 M được
chiếu sáng bởi bước sóng λ = 300 nm. Thí nghiệm cho thấy trung bình 1 photon bị hấp thụ
làm phân hủy 0,57 phân tử acid oxalic. Tính năng lượng bức xạ cần để phân hủy 1 mol acid
H2C2O4 + UO22+ CO + CO2 + H2O + UO22+
THE BASIC CONCEPTS 7

1.4. PHOTON ENERGY


 Energy required to excite the molecule and these can be determined from the absorption
or emission spectra of the molecule

E2 - E1 = h.ν
h: Planck constant
ν: radiation frequency
E1 , E2: energy in the initial and final state of the molecule

 The positions of the spectral lines can be determined by frequncy (ν), λ = c/ν (c = 3×1010

cm/s) or wave number ( = 1/ λ)


1 nm = 10-9 m = 10-7 cm = 1 mμ = 10 angstrom
 Ví dụ: bước sóng λ = 5000 angstrom tương ứng với tần số

. .
.

 Wave number:

 Photon energy:
. , . . × . .
.
THE BASIC CONCEPTS 8

1.5. PHOTOSYNTHETIC REACTION


Ví dụ: khi được mùa có thể thu hoạch 5 tấn chất hữu cơ khô trên 1 ha trong 1 năm. Hãy tính
hiệu suất φ chuyển quang năng thành hóa năng, cho biết thiêu nhiệt của chất hữu cơ là ∆H =
4.103 kcal/kg ; mặt trời chiếu trung bình 8 giờ/ngày với cường độ ánh sáng I = 10 kcal/phút.m2
KINETIC OF PHOTOCHEMICAL PROCESSES 9

2.1 DETERMINE THE LIFETIME ( 𝒐 ) OF THE EXCITED STATE


 Assume that, The excited singlet state, S1, is decayed by the fluorescence pathway
𝒌
𝟏 𝐨

 This deactivated process is referred to as a first order reaction:

 Lifetime of the excited state is the time required for the number of initially excited
molecules to decrease e times.
𝒐
KINETIC OF PHOTOCHEMICAL PROCESSES 10

2.2. MECHANISM OF DECAY OF EXCITED SINGLET STATES


 Consider the formation and decay of excited singlet states (S1)
KINETIC OF PHOTOCHEMICAL PROCESSES 11

2.2. MECHANISM OF DECAY OF EXCITED SINGLET STATES


 Quantum yield of fluorescence:

 Fluorescence lifetime:
BÀI TẬP

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