Photochemical Reactions — Light-Driven Chemistry

25개의 반응

Photochemical reactions are initiated by the absorption of light (photons) rather than heat. When a molecule absorbs a photon with sufficient energy, an electron is promoted to an excited state, making the molecule more reactive than in its ground state. Photochemistry governs processes as diverse as photosynthesis, vision, photography, atmospheric ozone chemistry, and the degradation of plastics in sunlight.

반응 메커니즘

The Grotthuss-Draper law states that only absorbed light can cause chemical change. The Stark-Einstein law states that each molecule undergoing photochemical change absorbs exactly one photon (primary process). After absorption, the excited molecule can undergo several pathways: fluorescence (re-emit light), internal conversion (convert to heat), intersystem crossing (change spin state to a longer-lived triplet state), or chemical reaction. Quantum yield measures the efficiency — moles of product per moles of photons absorbed.

일상 속 사례

Sunburn is a photochemical reaction — UV-B light damages DNA in skin cells. Sunscreen absorbs UV photons before they reach skin. Photosynthesis uses chlorophyll to absorb red and blue light, driving the reaction 6CO2 + 6H2O -> C6H12O6 + 6O2. Photography (both film and digital) relies on photochemical conversion of light into chemical or electrical signals.

산업적 중요성

Semiconductor lithography uses photochemical reactions in photoresists to pattern circuits at nanometer scales — enabling modern microchips. UV curing of coatings and adhesives is faster and more energy-efficient than thermal curing. Photocatalysis using titanium dioxide can break down pollutants in water and air. Solar cells use photovoltaic effects (related to photochemistry) to generate over 1,300 TWh of electricity globally.

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Safety Note

UV light sources used in photochemistry can cause severe eye and skin damage. Always use UV-blocking goggles and shields. Some photochemical reactions generate reactive oxygen species (singlet oxygen, hydroxyl radicals) that are highly toxic. Store photosensitive reagents in amber bottles away from light.

광합성

6CO₂ + 6H₂O → C₆H₁₂O₆ + 6O₂

The most important photochemical reaction on Earth. Plants, algae, and cyanobacteria use chlorophyll to capture sunlight and convert carbon dioxide …

흡열 · ΔH = 2803.0 kJ

스파이로피란의 광변색

Spiropyran (colorless) → Merocyanine (colored)

UV light causes the C–O bond in spiropyran to break, opening the ring to form the planar, conjugated merocyanine isomer …

흡열 · 가역 반응

아크릴레이트의 광중합

n CH₂=CHCOOR → [–CH₂–CH(COOR)–]ₙ

UV or visible light activates a photoinitiator that generates free radicals, which then initiate chain polymerization of acrylate monomers. The …

발열 · ΔH = -78.0 kJ

과산화수소의 광분해

H₂O₂ → 2OH·

UV light (< 300 nm) cleaves the O–O bond in hydrogen peroxide to generate two hydroxyl radicals, among the most …

흡열 · ΔH = 213.0 kJ

브로민화은의 광분해

2AgBr → 2Ag + Br₂

Silver bromide is more photosensitive than silver chloride and was the primary photosensitive material in photographic film. Blue and UV …

흡열 · ΔH = 199.0 kJ

아조벤젠의 광이성질화

trans-Azobenzene → cis-Azobenzene

UV light (340 nm) converts the thermodynamically stable trans isomer of azobenzene to the cis form through rotation around the …

흡열 · ΔH = 50.0 kJ · 가역 반응

염화은의 광분해

2AgCl → 2Ag + Cl₂

Silver chloride darkens upon exposure to light as photons provide enough energy to reduce Ag⁺ to metallic silver. This photosensitivity …

흡열 · ΔH = 254.0 kJ

반딧불이 생물발광 (루시페린 산화)

Luciferin + ATP + O₂ → Oxyluciferin + AMP + PPᵢ + CO₂ + hν

Firefly luciferase catalyzes the ATP-dependent oxidation of luciferin, producing oxyluciferin in an electronically excited state that emits yellow-green light (560 …

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염료감응 태양전지 (그레첼 전지)

Dye + hν → Dye* → Dye⁺ + e⁻ (into TiO₂)

In a Grätzel cell, a ruthenium dye absorbs sunlight and injects an electron into the conduction band of nanocrystalline TiO₂. …

흡열 · 가역 반응

자외선에 의한 오존 분해

2O₃ → 3O₂

UV-C radiation (< 240 nm) and UV-B (240–320 nm) break ozone back into molecular oxygen and atomic oxygen. This absorption …

발열 · ΔH = -285.4 kJ

자외선에 의한 오존 생성

3O₂ → 2O₃

Ultraviolet radiation (wavelength < 240 nm) splits O₂ molecules in the stratosphere. The resulting oxygen atoms combine with intact O₂ …

흡열 · ΔH = 285.4 kJ · 가역 반응

레티날의 시스-트랜스 이성질화

11-cis-Retinal → all-trans-Retinal

When a photon strikes rhodopsin in rod cells of the retina, it causes the 11-cis-retinal chromophore to isomerize to the …

흡열

엽록소 형광

Chlorophyll + hν (blue/red) → Chlorophyll* → Chlorophyll + hν (red)

Chlorophyll absorbs blue (430 nm) and red (660 nm) light, reaching an excited singlet state. Most energy is transferred to …

발열 · 가역 반응

루미놀 화학발광

C₈H₇N₃O₂ + H₂O₂ → 3-aminophthalate + N₂ + hν (blue light)

Luminol reacts with hydrogen peroxide in the presence of a catalyst (typically iron from hemoglobin in blood) to produce 3-aminophthalate …

발열 · ΔH = -300.0 kJ

에폭시 수지의 자외선 경화

Epoxy monomer + Photoinitiator → Cross-linked polymer

Cationic photoinitiators generate strong acids upon UV exposure, which catalyze the ring-opening polymerization of epoxy groups. Unlike free-radical photopolymerization, cationic …

발열 · ΔH = -95.0 kJ

염소 기체의 광해리

Cl₂ → 2Cl·

UV or visible light (< 500 nm) cleaves the Cl–Cl bond homolytically to produce two chlorine free radicals. This is …

흡열 · ΔH = 242.6 kJ

물의 광분해 (진공 자외선)

H₂O → H· + OH·

Vacuum UV radiation (< 185 nm) directly dissociates water molecules into hydrogen and hydroxyl radicals. This reaction is significant in …

흡열 · ΔH = 498.0 kJ

광전 효과 (세슘)

Cs + hν → Cs⁺ + e⁻

Photons with energy exceeding the work function of cesium (2.1 eV, wavelength < 590 nm) eject electrons from the metal …

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광화학 고리화 첨가 ([2+2])

2 CH₂=CH₂ → Cyclobutane

UV light promotes one alkene to its excited state, allowing a symmetry-forbidden [2+2] cycloaddition that cannot occur thermally according to …

발열 · ΔH = -109.0 kJ

CO₂의 메탄올 광환원

CO₂ + 3H₂O → CH₃OH + 3/2 O₂

Photocatalysts can reduce CO₂ to methanol using sunlight and water, mimicking photosynthesis to produce liquid fuel. Copper-modified TiO₂ and other …

흡열 · ΔH = 727.0 kJ

피부에서의 비타민 D₃ 광합성

7-Dehydrocholesterol → Previtamin D₃ → Vitamin D₃

UV-B radiation (280–315 nm) converts 7-dehydrocholesterol in the skin to previtamin D₃ through a photochemical ring-opening reaction. Previtamin D₃ then …

흡열

광화학 스모그 생성 (NO₂ 광분해)

NO₂ → NO + O·

Sunlight (< 420 nm) photolyzes nitrogen dioxide to produce nitric oxide and an oxygen atom. The oxygen atom then reacts …

흡열 · ΔH = 305.0 kJ

광촉매 NOx 제거

NOₓ + O₂ + H₂O → HNO₃

TiO₂ photocatalyst on building surfaces oxidizes nitrogen oxides (NOx) from vehicle exhaust to nitric acid (HNO₃), which is then washed …

발열 · ΔH = -206.0 kJ

광촉매 물 분해 (TiO₂)

2H₂O → 2H₂ + O₂

Titanium dioxide absorbs UV light and generates electron-hole pairs that can split water into hydrogen and oxygen. Discovered by Fujishima …

흡열 · ΔH = 572.0 kJ

TiO₂에 의한 메틸렌 블루 광분해

C₁₆H₁₈ClN₃S + TiO₂ + hν → CO₂ + H₂O + degradation products

TiO₂ photocatalysis generates hydroxyl radicals and superoxide ions that mineralize organic pollutants like methylene blue into CO₂, water, and simple …

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