일반화학2 헬프데스크

(기말고사)

2016.12.18
화학과 학생회

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시작하기 전에..
• 저희는 화학과 학생회입니다.

• 저희는 이런 단체입니다.

• 그래서 헬프데스크를 준비하게 되었습니다.

• 모두 파이팅입니다.

• 화학과 오신 분?

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부탁드립니다!
• 많이 부족할 수 있습니다.

• 강의 자료의 모든 내용을 설명하지는 않습니다.

• 어느 정도 배경 지식을 가진 학생들을 대상으로 만들었습니다.

• This session will be given in Korean.

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수업 계획
• 19:00 ~ 21:00 (120분) – 7, 23, 20.4단원 이론 설명

• 21:00 ~ 21:30 (30분) – 휴식시간 및 질문, 답변

• 21:30 ~ 23:30 (120분) – 8, 17단원 이론 설명

• 23:30 ~ - 질문, 답변

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기말고사 범위 한 눈에 보기

Organic chemistry + Inorganic chemistry + Electrochemistry

Chapter 7
Bonding in Organic Molecules

Chapter 20.4
Organic Chemistry Nuclear Magnetic Resonance Spectroscopy

Chapter 23
Polymeric Materials and Soft Condensed Matter

Chapter 8
Inorganic Chemistry Bonding in Transition Metal Compounds and Coordination Complexes

Chapter 17
Electrochemistry Electrochemistry

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 Chapter 7
Bonding in Organic Molecules

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7단원 한 눈에 보기
• Simplest organic molecules : Hydrocarbons

• Cyclic alkanes

• Isomerism

• Mechanisms in organic reaction

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Simplest organic molecule : Hydrocarbons
• Classes of organic molecules

Similar structures share similar properties

Electron rich/poor(O, N, X, …) - enhanced reactivity

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Simplest organic molecule : Hydrocarbons
• Hydrocarbons : alkane, alkene, alkyne

~ene? (alkene)

~yne? (alkyne)

~ol? (alcohol)

~ene? (alkene)

CnH2n+2 CnH2n CnH2n-2

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Simplest organic molecule : Hydrocarbons
• Basic properties : Boiling point

Dispersion force is dominant

Molecular weight + Surface area

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Simplest organic molecule : Hydrocarbons
• Basic properties : Geometry and Bond rotation

Hybridization? (sp3, sp2, sp)

Free rotation at room Temp

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Simplest organic molecule : Hydrocarbons
• Basic properties : Geometry and Bond rotation

at room Temp

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Cyclic alkanes
• CnH2n but saturated

Closed ring - each carbon has 2 hydrogens

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Cyclic alkanes
• Strain in cyclic alkanes

C3H6, C4H8 unstable

C5H10, C6H12 stable

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Cyclic alkanes
• Cyclohexane : Chair form and Boat form

Chair form is more stable

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Cyclic alkanes
• Cyclohexane : Axial/Equatorial + Ring flipping

Ring flip is free at room Temp.

Axial <-> Equatorial

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Cyclic alkanes
• Cyclohexane : Axial/Equatorial + Ring flipping

Axial ≠ Equatorial

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Cyclic alkanes
• 2015 기출

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Isomerism
• Structural isomers

• Cis/trans isomers

• Optical isomers

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Isomerism
• Find all isomers of C5H12

• Find all isomers of C4H8

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Mechanisms in organic reaction
• Major premise in organic chemistry
1) Acid-Base reaction occurs first

2) (-) Charge attacks (+) charge (electron-rich attacks electron-poor)

3) Octet rule

4) Formation of stronger bond is favored (= Weakest bond is first broken)

5) Better leaving group is preferred

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Mechanisms in organic reaction
1. Synthesis of alkyl halides (Radical reaction)

1. UV : electronic transition (𝜎 → 𝜎 ∗ )

2. Which bond is the weakest?

3. Unstable radical - Tend to react

4. Concentration ratio and termination

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Mechanisms in organic reaction
2. Alkyl halide to alcohol

1. Acid-base reaction occurs first

2. (-) attacks (+)

3. Octet rule
CH3X + NaOH → CH3OH + NaX
4. Weakest bond is first broken

5. Leaving group stability : Cl- vs OH-

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Mechanisms in organic reaction
3. Alkene + halogen

1. Acid-base reaction occurs first

2. (-) attacks (+)

3. Octet rule

4. Weakest bond is first broken

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Mechanisms in organic reaction
4. Epoxide ring opening

1. Acid-base reaction occurs first

2. (-) attacks (+)

3. Octet rule

4. Weakest bond is first broken

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Mechanisms in organic reaction
5. Esters / Amides

1. Acid-base reaction occurs first

2. (-) attacks (+)

3. Octet rule

4. Weakest bond is first broken

Why body is made up of proteins?

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Mechanisms in organic reaction
• 2015 기출

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Mechanisms in organic reaction
• Isotope labeling

Mechanism?

What if carboxylic acid is labelled?

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 Chapter 23
Polymeric Materials and Soft Condensed Matter

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23단원 한 눈에 보기
• Polymers and polymerization mechanism

• Monomer and Polymer structures

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Polymers and polymerization mechanism
• Polymers

Many monomers join together

High molecular weight - solid

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 Polymers and polymerization mechanism
• Polymerization : Radical polymerization

Initiation - Propagation (repeated) - Termination

Concentration ratio leads propagation

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Polymers and polymerization mechanism
• Polymerization : Condensation

Same mechanism in Chapter 7

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Monomer and Polymer structures
• Monomer structure for each polymers?

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Monomer and Polymer structures
• 2014 기출

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 Chapter 20.4
Nuclear Magnetic Resonance Spectroscopy

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20.4단원 한 눈에 보기
• Basic concepts of NMR

• Chemical shift

• Proton-proton coupling and splitting

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Basic concepts of NMR
• External magnetic field and nucleus spin

Nucleus has its own spin

External magnetic field splits nuclei into two energy state - absorption spectroscopy

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Basic concepts of NMR
• External magnetic field and nucleus spin

(i) Energy splitting increases with External magnetic field

(ii) Nucleus with odd mass can absorb energy

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Basic concepts of NMR
• Local magnetic field

Lenz’s law : electrons oppose external magnetic field

Beff = Bexternal - Bshielding

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Basic concepts of NMR
• Overall principles of NMR
1) External magnetic field makes energy splitting -> spectroscopy

2) Electrons produce opposite magnetic field

3) Different electron density makes different Beff -> Different peaks

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Basic concepts of NMR
• Overall principles of NMR

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Chemical shift
• NMR peaks need to be scaled relatively

100 J absorption with 300 MHz NMR

How much for 600 MHz NMR?

300 MHz NMR 600 MHz NMR

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Chemical shift
• Reference peak : TMS

Tetramethylsilane (TMS) : Reference peak

H has high electron density

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Chemical shift
• Reference peak : TMS

TMS : 1,000,000
Certain proton : 1,000,001

-> 1 ppm

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Basic concepts of NMR
• Overall principles of NMR

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Proton-proton coupling and splitting
• Nearby protons affect absorption

Same protons do not couple

Only nearby protons can couple

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Proton-proton coupling and splitting
• 2014 기출

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Proton-proton coupling and splitting
• 2014 기출

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수업 계획
• 19:00 ~ 21:00 (120분) – 7, 23, 20.4단원 이론 설명

• 21:00 ~ 21:30 (30분) – 휴식시간 및 질문, 답변

• 21:30 ~ 23:30 (120분) – 8, 17단원 이론 설명

• 23:30 ~ - 질문, 답변

50
수업 계획
• 19:00 ~ 21:00 (120분) – 7, 23, 20.4단원 이론 설명

• 21:00 ~ 21:30 (30분) – 휴식시간 및 질문, 답변

• 21:30 ~ 23:30 (120분) – 8, 17단원 이론 설명

• 23:30 ~ - 질문, 답변

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 Chapter 8
Bonding in Transition Metal Compounds and Coordination Complexes

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8단원 한 눈에 보기
• History of coordination complexes

• Some principles in coordination complexes

• Isomers in coordination complexes

• VBT, CFT, LFT of Oh complexes

• Other structures : Td and sq-pl complexes

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History of transition metal complexes
• First suggested by Alfred Werner

Amount of AgCl(s) precipitate differed

Free Cl vs metal-bounded Cl

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History of transition metal complexes
• First suggested by Alfred Werner

Free Cl- : AgCl formation

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Some principles in coordination complexes
• Hard-soft acid/base (HSAB)

Hard-Hard, Soft-Soft interaction is stronger

Hard : Small, highly charged

Soft : Big, weakly charged

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Some principles in coordination complexes
• Examples : Predict the direction of equilibrium

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Some principles in coordination complexes
• Examples : Hair and heavy metal

Sulfur atom in hair : capture heavy metals

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Some principles in coordination complexes
• Chelate effect : Entropy effect

Ethylenediamine (en)

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Some principles in coordination complexes
• Chelate effect : Entropy effect

EDTA : Ethylene diamine tetra acetate

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Isomers in coordination complexes

MA4B2 : 2 isomers (cis, trans)

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VBT, CFT, LFT of Oh complexes

• VBT : Valence Bond Theory

(ii) Make 6 empty rooms

(iii) Orbital hybridization

<Limitations>

High spin, Low spin

Cr(NH3)63+ Co(NH3)63+ Colors in metal complexes

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VBT, CFT, LFT of Oh complexes

• CFT : Crystal Field Theory

(i) Repulsion occurs

(ii) Spherical field vs Crystal field

(iii) Splitting occurs

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VBT, CFT, LFT of Oh complexes

• CFT : Crystal Field Theory

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VBT, CFT, LFT of Oh complexes

• CFSE

CFSE : Stabilization compared to spherical field

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VBT, CFT, LFT of Oh complexes

• Limitations of CFT

<Improvements>

Color, magnetic properties, etc.

<Limitations>

Why does this series occur?

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VBT, CFT, LFT of Oh complexes

• LFT : Ligand Field Theory

LFT : MO approach of metal complexes

MO : Energy + Symmetry

(i) Ligands come through axial direction

(ii) What orbitals can form bonds?

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VBT, CFT, LFT of Oh complexes

• LFT : Ligand Field Theory

Comparison with CFT

- Orbital splitting?

- Fate of metal electrons?

- Orbital types?

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VBT, CFT, LFT of Oh complexes

• LFT and pi interactions – pi donor

Splitting decreases

F-, Cl-, Br-, I-, etc.

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VBT, CFT, LFT of Oh complexes

• LFT and pi interactions – pi acceptor

Splitting increases

CO, CN-, etc.

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VBT, CFT, LFT of Oh complexes

• Spectrochemical series - revisited

Halogen … O … N … C

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Other structures

• Tetrahedral(Td) structures

Td complexes are ‘always high spin’

(i) Less ligands

(ii) Indirect interactions

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Other structures

• Square planar(sq-pl) structures

Usually Td, but sq-pl favored when

(i) d8 complexes

(ii) Strong field ligand (Low spin)

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Practice problems
• 2015 기출

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Practice problems
• 2015 기출

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Chapter 17
Electrochemistry

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17단원 한 눈에 보기
• Redox reaction and coefficients
• Redox reactivity : Reduction potential
• Galvanic cell
• △G and △E : Latimer diagram
• Non-standard conditions : Nernst equation
• Electrolytic cell
• Other concepts

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Redox reaction and coefficients
• Redox reaction : Change in oxidation state

NOT a redox reaction

Redox reaction

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Redox reaction and coefficients
• Balancing redox reaction

(i) Oxidation number count

(ii) Atom number count (Half cell reaction)

(iii) Electron number count

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Redox reactivity : Reduction potential
• Redox reactivity

“Cu2+ + 2e → Cu”
“Cu2+ + 2e → Cu”
vs
vs
“Zn2+ + 2e → Zn” “Zn2+ + 2e → Zn”

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Redox reactivity : Reduction potential
• Redox reactivity : Reduction potential

∆𝐺 < 0 ∶ 𝑠𝑝𝑜𝑛𝑡𝑎𝑛𝑒𝑜𝑢𝑠 → 𝑊𝑜𝑟𝑘 𝑡𝑜 𝑜𝑢𝑡𝑠𝑖𝑑𝑒 𝐻𝑒𝑎𝑡, 𝑙𝑖𝑔ℎ𝑡, 𝑒𝑡𝑐

𝑛 𝑚𝑜𝑙 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑠 𝑓𝑙𝑜𝑤 𝑎𝑐𝑟𝑜𝑠𝑠 𝑝𝑜𝑡𝑒𝑛𝑡𝑖𝑎𝑙 𝑜𝑓 𝐸 → ∆𝐺 = −𝑛𝐹𝐸

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Redox reactivity : Reduction potential
• Redox reactivity : Reduction potential

More spontaneous : Higher E0

Less spontaneous : Smaller E0

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Galvanic cell
• Difference in redox reactivity : spontaneous reaction

Zn2+/Zn : -0.76V, Cu2+/Cu : +0.34V

(i) Reaction direction?

(ii) Cell potential?

(iii) Role of salt bridge?

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△G and △E : Latimer diagram
• Can we simply add/subtract E? – Latimer diagram

Relation between z and x, y

z (ii) z = (x + y) / 2

(iii) z = (x + 2y) / 3

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△G and △E : Latimer diagram
• Can we simply add/subtract E? – Latimer diagram

Relation between z and x, y

△G3 (ii) z = (x + y) / 2

(iii) z = (x + 2y) / 3
△G1 + △G2 = △G3

-n1FE1 - n2FE2 = -n3FE3

E3 = (n1E1 + n2E2) / n3

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△G and △E : Latimer diagram
• How can we simply add/subtract E in cells?

Overall : Cu2+ + Zn → Cu + Zn2+

△Gtotal = △GCu + △GZn

-nFEtotal = (-nFECu) + {-(-nFEZn)}

Etotal = Ecu - EZn

Meaning of (-) : reverse reaction

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Non-standard conditions : Nernst equation
• Spontaneity changes with concentration

-nFE = -nFE0 + RTlnQ

E = E0 - (RT/nF) lnQ

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Non-standard conditions : Nernst equation
• 2015 기출

(i) Calculate for each half cell reaction

(ii) Calculate at once

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Electrolytic cell
• Opposite of galvanic cell
• A+B → C+D produces E ↔ Higher than E needed to make C+D → A+B

• Nernst equation equally applied

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Other concepts
• Equilibrium constants in redox reaction

• Current, time, stoichiometry

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Electrolytic cell
• 2014 기출

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Electrolytic cell
• 2014 기출

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수업 계획
• 19:00 ~ 21:00 (120분) – 7, 23, 20.4단원 이론 설명

• 21:00 ~ 21:30 (30분) – 휴식시간 및 질문, 답변

• 21:30 ~ 23:30 (120분) – 8, 17단원 이론 설명

• 23:30 ~ - 질문, 답변

93