Lecture 3 pKa acidity and basicity
Acid-Base Balance and Disturbances(7)
6. Anion Gap (AG) 阴离子间隙 )
AG 指血浆中未测定的 阴离子 (UA) 与未测定的阳 之间的差值. 离子 (UC) 之间的差值
4. Effect of Cells 细胞的调节作用 Ion exchange between intracellular and extracellular fluids H＋-Na＋ exchange H＋-K＋→hypokalemia/ hyperkalemia Na＋-K＋ exchange Cl--HCO3- exchange
4. Buffer Base (BB) 缓冲碱 )
血液中一切具有缓冲作用的负离子的总 和 。 包括HCO3- 、 Hb- 、 HPO42- 和 Pr- 等 ， 正 包括 常值为45～ 常值为 ～52mmol/L（平均 mmol/L）。 （平均48 ） BB是反映代谢性因素指标 是反映代谢性因素指标 BB↓：代酸； BB↑：代碱。 ↓ 代酸； ↑ 代碱。
Respiratory acidosis
[HCO3-]
Respiratory factor
Respiratory alkalosis
[H2CO3]=α×PaCO2
代谢性因素
代谢性酸中毒 代谢性碱中毒
24 pH = pKa + log =6.1+lg 1.2 [H2CO3] =7.4
呼吸性因素
呼吸性酸中毒 呼吸性碱中毒
3. Respiratory regulation of acid-base balance 呼吸的调节
Regulation through central / peripheral chemoreceptors
通过中枢和外周化学感受器作用 PaCO2 ↑ /↓, pH ↓ /↑ ↓ ↑ ↓ Chemorecertor (+)/(-) )() ↓ Pulmonary ventilation ↑/ ↓ 肺泡通气量 ↓ PaCO2 ↓/ ↑
有机含氮化合物
1授课内容 Chapter 9 有机含氮化合物 学时数 6掌握比较含氮化合物碱性强弱的方法、胺与HNO 2的反应、重氮盐的放氮及偶联反应；理解杂环的芳香性及反应活性顺序； 了解生物碱的一般性质。
第一节 胺 Amines（胺的碱性、胺与HNO 2的反应）； 第二节 重氮和偶氮化合物Diazo and Azo Compounds （放氮和偶联反应）； 第三节 酰胺Amides （酸碱性、缩二脲反应）第四节 含氮杂环化合物Heterocycles （反应活性比较） 第五节 生物碱AlkaloidsP250/1, 4, 11, 15教材：《有机化学》张生勇主编。
高等教育出版社。
参考文献： 1．《基础有机化学》邢其毅等编。
第二版，高等教育出版社。
2．《Organic Chemistry 》Stephen J. et al. Academic Press3．《Fundamentals of Organic Chemistry 》（美）John McMurry 著 机械工业出版社教学目的（含重点，难点）主 要 内 容复习思考题参考文献教 材 教研室意见2教 学 内 容时间分配媒体选择第九章 有机含氮化合物含氮有机化合物 主要指分子中的氮原子和碳原子直接相连的化合物，也可以看成是烃分子中的一个或几个氢原子被含氮的官能团所取代的衍生物。
例如，生物碱、蛋白质、磺胺类药物等。
本章主要讨论胺(amine)、重氮化合物(diazo compound)、偶氮化合物(azo compound)、酰胺(amide)、含氮杂环化合物和生物碱(alkaloid)。
第一节 胺Amines一、胺的结构、分类和命名Structures, Classification and Nomenclature (一)胺的结构和分类胺：可看作是氨分子中的氢原子被烃基取代所生成的化合物。
通式:R-NH 2，R 2NH 或R 3N ，其中R 代表烃基，它们分属于伯、仲和叔胺。
有机化学01-Lecture
A polar covalent bond has a slight positive charge on one end and a slight negative charge on the other
A Polar Bond Has a Dipole Moment
A polar bond has a negative end and a positive end
The synthesis of the simple organic compound urea in 1828 showed that organic compounds can be prepared in the laboratory from non-living material.
Today, organic natural products are routinely synthesized in the laboratory.
Molecular weight: the sum of the atomic weights of all the atoms in the molecule
The Distribution of Electrons in an Atom
Quantum mechanics uses the mathematical equation of wave motions to characterize the motion of an electron around a nucleus.
Nitric Oxide Radical, Mammalian Signaling Agent
Radical
Carbocation
Carbene
Borane
对羟基苯甲酸pka值
对羟基苯甲酸pka值English Answer:pKa is a measure of the acidity or basicity of a chemical compound. It is defined as the negative logarithm of the acid dissociation constant (Ka), which is a measure of the tendency of the compound to donate a proton (H+).The pKa of para-hydroxybenzoic acid (p-HBA) is 4.56. This means that it is a weak acid, and it will onlypartially dissociate in water. The equilibrium constant for the dissociation of p-HBA is:p-HBA + H2O <=> H+ + p-HBA-。
The Ka for this reaction is:Ka = [H+][p-HBA-] / [p-HBA]The pKa is then:pKa = -log(Ka) = -log([H+][p-HBA-] / [p-HBA])。
The pKa of p-HBA can be used to calculate the pH at which it will be 50% dissociated. This is known as thehalf-equivalence point. The half-equivalence point is:pH = pKa + log([p-HBA-] / [p-HBA])。
At the half-equivalence point, the concentration of the acid and its conjugate base are equal.The pKa of p-HBA can also be used to calculate the buffer capacity of a solution. The buffer capacity is a measure of the ability of a solution to resist changes in pH. The buffer capacity is:β = d[H+] / d[p-HBA]The buffer capacity is greatest at the half-equivalence point.中文回答：pKa值是衡量化学化合物酸碱性的指标。
大学基础化学第三节酸碱理论ppt课件
6
➢(3) 在酸碱质子理论中，排除了盐的概念。 ➢(4) 酸碱质子理论体现了酸和碱这对矛盾
相互转化和相互依存的关系，并且扩大 了酸碱物质的范围。
7
（二）酸碱反应的实质
酸碱半反应式: 酸 H+ + 碱
例如HAc在水溶液中的存在两个酸碱半反应：
HC2O4-
HSO3-
H2PO4F-
HCOOAc-
HCO3-
碱 性 增 强
HPO42-
CO3 2 -
PO43- 16 OH-
(四) 拉平效应和区分效应
实验证明，HClO4、H2SO4、HCl和HNO3的 强度是有差别的，其强度顺序为 HClO4＞ H2SO4＞HCl＞HNO3。
HClO4＋H2O H2SO4＋H2O HCl＋H2O HNO3＋H2O
30
二、溶液的pH
物质均衡（MBE)： 它是指在一个平衡体 系中，某一给定组分的总浓度，等于各有 关组分平衡浓度之和。
例如：浓度为c(mol.L-1)的HAc溶液的物 质均衡 c(HAc)=[HAc]+[Ac-]
电荷均衡（CBE) ： 根据电中性原则，
溶液中正离子的总电荷数与负离子的总电
荷数恰好相等。
H3O+＋ClO4－ H3O+＋HSO4－ H3O+＋Cl－ H3O+＋NO3－
17
将各种不同强度的酸拉平到溶剂化质子 （在这里是水化质子H3O+）水平的效应称 为拉平效应(leveling effect)。具有拉平效应 的溶剂称为拉平性溶剂。
18
而冰醋酸可把上述这些酸的强度区分开来，溶 剂 的 这 种 作 用 称 为 区 分 效 应 (differentiating effect)，这种溶剂便称为区分溶剂。 一般而言，酸性溶剂可以对酸产生区分效应， 而对碱产生拉平效应，碱性溶剂则可对碱产生 区分效应，而对酸产生拉平效应。
高等有机化学教案4酸和碱acidandba
17–2
17 Acid and Base
5
Problems with B-L theory
The theory works very nicely in all protic solvent, but fails to explain acid-base behavior in aprotic solvents and non-solvent situations. A more general concept on acid and base was proposed by G.N. Lewis at about the same time Bronsted-Lowry theory was proposed.
The fundamental concept: (Text PHH: 17-1)
Acid - any substance which delivers hydrogen ion (H+) to the solution. HA H+ + A¯
Base - any substance which delivers hydroxide ion (OH¯ ) to the solution. BOH X+ + OH¯
17 Acid and Base
4
Brønsted-Lowry theory of acids and bases
An acid is a substance from which a proton can be removed. Acids are proton donors.
A base is a substance that can remove a proton from an acid. Bases are proton acceptors. Because of strong desire for protons, bases rip protons off acids.
IChO国际化学奥林匹克竞赛考试大纲
SYLLABUS OF THEINTERNATIONAL CHEMISTRY OLYMPIADPart I Theoretical partLevel 1: These topics are included in the overwhelming majority of secondary school chemistry programs and need not be mentioned in the preparatory problems.Level 2: These topics are included in a substantial number of secondary school programs and maybe used without exemplification in the preparatory problems. Level 3: These topics are not included in the majority of secondary school programs and can only be used in the competition if examples are given in the preparatory problems.1.The atom1.1.Introduction1.1.1.Counting of nucleons 11.1.2.Isotopes 1 1.2.The hydrogen atom1.2.1.Concept of energy levels 11.2.2.Shape of s-orbitals 11.2.3.Shape and orientation of p-orbitals 11.2.4.Shape and orientation of d -orbitals 31.2.5.Understanding the simplest Schrodinger equation 31.2.6.Square of the wave function and probability 31.2.7.Quantum numbers (n, l, m l) 3 1.3.Radioactivity1.3.1.Types of radioactivity 11.3.2.Radioactive decay 11.3.3.Nuclear reactions 22.Chemical bonding2.1.VSEPR - Simple molecular structures with2.1.1.no more than four electron pairs about central atom 12.1.2.with central atom exceeding the “octet rule”3 2.2.Delocalization and resonance3 2.3.Hybrid orbital theory3 2.4.Molecular orbital theory2.4.1.molecular orbital diagram (H2 molecule) 32.4.2.molecular orbital diagram (N2 and O2 molecules) 32.4.3.bond orders in O2, O2-, O2+ 32.4.4.unpaired electrons and paramagnetism 33.Chemical calculations3.1.1.Balancing equations 13.1.2.Stoichiometric calculations 13.1.3.Mass and volume relations (including density) 13.1.4.Empirical formula 13.1.5.Avogadro’s number 13.1.6.Concentration calculations 14.Periodic trends4.1.Electron configuration 4.1.1. Pauli exclusion principle14.1.2.Hund’s Rule 14.1.3.Main group elements 14.1.4.Transition metal elements 14.1.nthanide and actinide metals 3 4.2.Electronegativity 1 4.3.Electron affinity 2 4.4.First ionization energy 1 4.5.Atomic size 1 4.6.Ion size 14.7.Highest oxidation number 15.Inorganic Chemistry5.1.Introduction5.1.2.Trends in physical properties of elements (Main groups)5.1.2.1.melting point 15.1.2.2.boiling point 15.1.2.3.metal character 15.1.2.4.magnetic properties 35.1.2.5.electrical conductivity 25.1.3.Oxidation number 15.1.4.Nomenclature 5.1.3.1. main group compounds15.1.4.1.transition metal compounds 15.1.4.2.simple metal complexes 3 5.2.Groups 1 and 2 5.2.1. Trend in reactivity of (heavy elements more reactive) 15.2.2.Products of reaction with 5.2.2.1. water15.2.2.1.halogens 15.2.2.2.oxygen 25.2.3.Basicity of oxides 15.2.4.Properties of hydrides 35.2.5.Other compounds, properties and oxidation states 3 5.3.Groups 13 - 18 and Hydrogen5.3.2.Binary molecular compounds of hydrogen 5.3.1.1. Formulae 15.3.2.1.Acid-base properties of CH4, NH3, H2O, H2S 15.3.2.2.Other properties 35.3.3.P block elementsGroup 13 (Boron group) 5.3.2.1 The oxidation state of boron andaluminium in their 1 oxides and chlorides is +35.3.3.1.The acid-base properties of aluminium 2oxide/hydroxide5.3.3.2.Reaction of boron(III) oxide with water 35.3.3.3.Reaction of boron(III) chloride with water 35.3.3.4.Other compounds, properties and oxidation states 35.3.4.Group 14 (Carbon group)5.3.4.1.The oxidation state of Si in its chloride and oxide is 1 +45.3.4.2.The +2 and +4 oxidation states of carbon, tin and 2 lead, theacid-base and redox properties of the oxides and chlorides5.3.4.3.Other compounds, properties and oxidation states 35.3.5.Group 15 (Nitrogen group)5.3.5.1.Phosphorus(+5) oxide and chloride, and their 2 reaction withwater5.3.5.2.Phosphorus(+3) oxide and chloride, and their 2 reaction withwater5.3.5.3.Oxides of nitrogen a. Reaction of NO to form NO2 1b.Dimerization of NO2 1c.Reaction of NO2 with water 15.3.5.4.Redox properties of a. HNO3 and nitrates 1b. HNO2 and NH2NH2 35.3.5.5.Bi(+5) and Bi( + 3) 35.3.5.6.Other compounds, properties and oxidation states 35.3.6.Group 16 (Oxygen group)5.3.6.1.The +4 and +6 oxidation states of sulfur, reaction 1 of theiroxides with water, properties of their acids5.3.6.2.Reaction of thiosulfate anion with I2 35.3.6.3.Other compounds, properties and oxidation states 35.3.7.Group 17 (Halogens)5.3.7.1.Reactivity and oxidant strength decreases from F2 1to I25.3.7.2.Acid-base properties of the hydrogen halides 15.3.7.3.The oxidation state of fluorine in its compounds is 1 -15.3.7.4.The -1, +1, +3, +5, +7 oxidation states of chlorine 15.3.7.5.Mononuclear oxoanions of chlorine 25.3.7.6.Reactions of halogens with water 35.3.7.7.Reaction of Cl2O and CI2O7 with water 35.3.7.8.Other compounds, properties and oxidation states 35.3.8.Group 18 (Rare gases) 3 5.4.Transition elementsmon oxidation states of common transition metals: 1Cr(+2), Cr(+3) Mn(+2), Mn(+4), Mn(+7) Ag(+1) Fe(+2), Fe(+3)Co(+2) Zn(+2) Hg(+1), Hg(+2) Cu(+1), Cu(+2) Ni(+2)5.4.3.Colours of ions listed above in aqueous solution 25.4.4.Insolubility of Ag, Hg and Cu in HCl 25.4.5.M2+ arising by dissolution of the other metals in HCl 25.4.6.Cr(OH)3 and Zn(OH)2 are amphoteric and the other +2 2oxides/hydroxides of the metals listed above are basic5.4.7.MnO4- and Cr2O72- are strong oxidants in acid solution 15.4.8.pH dependence of products of MnO4- acting as oxidant 25.4.9.Interconversion between CrO42- and Cr2O72- 35.4.10.Other compounds, properties and oxidation states 3 nthanides and actinides3 5.6.Coordination chemistry including stereochemistry5.6.2.Definition of coordination number 15.6.3.Writing equations for complexation reactions given all 1formulae5.6.4.Formulae of common complex ions5.6.4.1.Ag(NH3)2+ 15.6.4.2.Ag(S2O3)23- 35.6.4.3.FeSCN2+ 35.6.4.4.Cu(NH3)42+ 15.6.4.5.Other complex ions 35.6.5.(6.5) Ligand field theory (e g and 12g terms, high and low spin) 35.6.6.Stereochemistry5.6.6.1.(6.7) cis and trans35.6.6.2.enantiomers 3 5.7.Selected industrial processes5.7.2.Preparation of H2SO4 15.7.3.PreparationofNH3 15.7.4.PreparationofNa2cO3 25.7.5.PreparationofCl2 and NaOH 25.7.6.PreparationofHNO3 26.Physical chemistry6.1.Gases6.1.2.Ideal gas law 16.1.3.van der Waal’s gas law36.1.4.definition of partial pressure 26.1.5.Dalton’s Law3 6.2.Thermodynamics6.2.2.First Law6.2.2.1.Concept of system and surroundings 26.2.2.2.Energy, heat and work 26.2.3.Enthalpy6.2.3.1.Relationship between internal energy and enthalpy 36.2.3.2.Definition of heat capacity 26.2.3.3.Difference between C p and C v (ideal gas only) 36.2.3.4.Enthalpy is a state property (Hess’s Law) 26.2.3.5.Born-Haber cycle for ionic compounds 3e of standard formation enthalpies 26.2.3.7.Enthalpies of solution and solvation 36.2.3.8.Bond enthalpies (definition and use) 26.2.4.Second Law (Entropy and Free Energy)6.2.4.1.Entropy definition (dq / T)36.2.4.2.Entropy and disorder 36.2.4.3.Entropy definition (S = k ln W) 36.2.4.4.Gibbs energy definition (A G = A H - T A S) 3ing A G to predict direction of natural change 36.2.4.6.Relationship between A G° and equilibrium constant K3 6.3.Equilibrium6.3.2.Acid-base6.3.2.1.Arrhenius definitions of acids and bases 16.3.2.2.Bronsted-Lowry definitions 16.3.2.3.Conjugate acids and bases 16.3.2.4.pH definition 16.3.2.5.K w definition 16.3.2.6.K a and K b as a measure of acid and base strength 16.3.2.7.Acidity or basicity of ions 16.3.2.8.Calculation of pH from p K (weak acid) 1a6.3.2.9.Calculation of pH of a simple buffer solution 26.3.3.Gas phase6.3.3.1.Equilibrium constant in partial pressures 36.3.3.2.Relating K and K c 36.3.4.Solubility P6.3.4.1.Solubility constant (product) definition (K s p) 26.3.4.2.Calculation of solubility in water from K 2s sppleximetricplex formation constant (definition) 36.3.5.2.Problems involving compleximetric equilibria 36.3.5.3.Lewis acids and bases 36.3.5.4.Hard and soft Lewis acids and bases 36.3.6.Phase6.3.6.1.Temperature dependence of vapour pressure 36.3.6.2.Clausius-Clapeyron equation 36.3.6.3.Single component phase diagramsa.triple point 3b.critical point 36.3.6.4.liquid-vapour systema.ideal and nonideal systems 3b.diagram 3e in fractional distillation 36.3.6.5.Henry’s Law36.3.6.6.Raoult’s Law36.3.6.7.Deviation from Raoult,s Law 36.3.6.8.Boiling point elevation 36.3.6.9.Freezing point depression 36.3.6.10.Osmotic pressure 36.3.6.11.Partition coefficient 36.3.6.12.Solvent extraction 36.3.7.Multiple6.3.7.1.Calculation of pH for multiprotic acids 36.3.7.2.Calculation of pH for weak acidmixtures 3 6.4.Electrochemistry6.4.2.Electromotive force (definition) 16.4.3.First kind electrodes 16.4.4.Standard electrode potential 16.4.5.Nernst equation 36.4.6.Second kind electrodes 36.4.7.Relationship between G and electromotive force 37.Chemical kinetics (Homogeneous reactions)7.1.Introduction7.1.2.Factors affecting reaction rate 17.1.3.Reaction coordinates and thebasic idea of a transition state 17.2.Rate law7.2.2.Differential rate law 27.2.3.Concept of reaction order 27.2.4.Rate constant definition 27.2.5.First order reactions7.2.5.1.Dependence of concentration on time 37.2.5.2.Concept of half life 37.2.5.3.Relationship between half life and rate constant 37.2.5.4.Calculation of first order rate constant from a. differential rate law 3b. integrated rate law 37.2.5.5.Rate constant for second and third order reactions 3 7.3.Reaction mechanisms7.3.2.Concept of molecularity 37.3.3.Rate-determining step 37.3.4.Basic concepts of collision theory 37.3.5.Opposing parallel and consecutive reactions 37.3.6.Arrhenius’s law37.3.6.1.Definition of activation energy 37.3.6.2.Calculation of activation energy 38.Spectroscopy8.1.UV/visible8.1.2.Identification of aromatic compound 38.1.3.Identification of chromophore 38.1.4.Dyes: colour vs structure 38.1.5.Beer’s Law3 8.2.Infrared8.2.2.Interpretation using a table of frequencies 38.2.3.Recognition of hydrogen bonds 3 8.3.x-Ray8.3.2.Bragg,s Law 38.3.3.Concept of8.3.3.1.coordination number 38.3.3.2.unit cell 38.3.4.Solid structures8.3.4.1.NaCl 38.3.4.2.CsCl 38.3.4.3.metals 38.4.1.General Concepts 8.4.1.1. chemical shift38.4.1.2.spin-spin coupling and coupling constants 38.4.1.3.integration 38.4.2.Interpretation of a simple 1H spectrum (like ethanol) 38.4.3.Identification of o- and p-disubstituted benzene 38.4.4.Interpretation of simple spectra of 13C (proton decoupled) and 3other 1/2 spin nuclei8.5. Mass spectrometry8.5.1.1.Recognition of molecular ion 38.5.1.2.Recognition of fragments with the help of a table 38.5.1.3.Recognition of typical isotope distribution 3anic Chemistry9.1.Introduction 9.1.1. (3.1.1) Alkane naming (IUPAC) 19.1.2.Trends in boiling points of9.1.2.1.(3.1.3) alkanes with structure 19.1.2.2.(3.7.1) alcohols vs ethers due to hydrogen-bonding 19.1.3.(3.3.1, 3.4.1) Geometry at singly, doubly, and triply bonded 1 carbon9.1.4.Identification of common functional groups 19.1.5.Isomerism of alkenes 9.1.5.1. cis - trans19.1.5.1.E/ Z39.1.6.Enantiomers9.1.6.1.Optical activity 29.1.6.2.R/S nomenclature 3 9.2.Reactivity9.2.2.Alkanes9.2.2.1.reaction with halogens a. products 1b. free radical mechanism (initiation,termination) 29.2.2.2.Cycloalkanes a. names 2b.Strain in small rings 3c.chair/boat conformations of cyclohexane 39.2.3.Alkenes9.2.3.1.Products from Br2, HBr and H2O/H+ 19.2.3.2.Markownikoff’s rule 29.2.3.3.Mechanism involving carbocation intermediates 39.2.3.4.Relative stability of carbocations 39.2.3.5.1,4 addition to dienes 39.2.4.Alkynes 9.2.3.1. Acidity relative to alkenes39.2.4.1.Differences in chemical properties from alkenes 29.2.5.Benzene 9.2.4.1. formula19.2.5.1.stabilization by resonance 19.2.5.2.electrophilic substitution (nitration, halogenation)a.directing effect of first substituent 3b.effect of first substituent on reactivity 3c.explanation of substituent effects 39.2.6.Halogen compounds 9.2.5.1. Nomenclature of monofunctional19.2.6.1.Substitution reactionsa.giving alcohols 3b.in which halogen is exchanged 3c.reactivityi.primary i/s secondary i/s tertiary 3ii.aliphatic /s aromatic 3d.S N1 and S N2 mechanisms 39.2.6.2.Elimination reactions 2petition of elimination and substitution 2 9.2.7.Alcohols 9.2.6.1. Nomenclature of monofunctional1parison of acidity of alcohols and phenols 29.2.7.2.Dehydration to alkenes 19.2.7.3.Esters with inorganic acid 29.2.7.4.Oxidation reactions 1 9.2.8.Aldehydes and ketones 9.2.7.1. Nomenclature of monofunctional19.2.8.1.Oxidation of aldehydes 19.2.8.2.Reduction to alcohols (LiAlH4, NaBH4) 39.2.8.3.Keto/enol tautomerism 39.2.8.4.Nucleophilic addition reactions witha.HCN 3b.RNH2 (R = alkyl, HO, NH2) 3c.enolate anions (aldol condensation) 3d.alcohols to form acetals/ketals 3e.Grignard reagents 39.2.9.Carboxylic acids and their derivatives 9.2.8.1.Nomenclature of carboxylicacids and their 2 derivatives (esters, acid halides, amides)9.2.9.1.Acidity strength related to inductive effects 39.2.9.2.Preparation of carboxylic acids by hydrolysis of a. esters(including soaps) 1b.amides 2c.nitriles 39.2.9.3.Reaction of carboxylic acids a. with alcohols to form esters 1b.to form acid chlorides 3c.to form anhydrides 39.2.9.4.Reaction of acid chlorides to form amides 39.2.9.5.Mechanism of esterification 39.2.9.6.Multifunctional acids (hydroxyacids, ketoacids) 39.2.9.7.Polycarboxylic acids 39.2.10.Amines9.2.10.1.Nomenclaturea.simple amines 1b.recognition of primary, secondary, tertiary 19.2.10.2.Basicitya.As a property of an amine 1parison of basicity of aliphatic and aromatic 3parison of basicity of amines and amides 3d.Preparation of aminesi.from halides 3ii.from aromatic nitro compounds 3iii.from amides (by hydrolysis) 39.2.10.3.Diazotizationa.of aliphatic amines 3b.of aromatic amines 310.Polymers10.1.Synthetic10.1.2.Addition polymers10.1.2.1.polystyrene 210.1.2.2.polyethene 110.1.2.3.chain mechanism of formation 210.1.3.Condensation polymers10.1.3.1.polyesters 210.1.3.2.polyamides 210.1.4.Silicones 310.1.5.Concept of cross-linking and its affect on properties 3 10.2.. Natural10.2.2.Silicates10.2.3.Rubber11.Biochemistry11.1.Carbohydrates11.1.2.Glucose and fructose11.1.2.1.chain formulae 111.1.2.2.Fischer projections 211.1.2.3.Haworth formulae 311.1.3.Difference between starch and cellulose 211.1.4.Difference between a- and p- D glucose 2 11.2.Fats11.2.2.Structure of fats in relationship to properties 211.2.3.Formula of glycerol 1 11.3.Nitrogen-containing Compounds of Biological Importance11.3.2.Amino acids 11.3.1.1. Ionic structure111.3.2.1.Isoelectric point 311.3.2.2.20 amino acids (classification with structures 2provided)11.3.2.3.Separation by electrophoresis 311.3.2.4.The peptide linkage 111.3.3.Proteins11.3.3.1.Primary structure 111.3.3.2.-S-S- bridges 311.3.3.3.Sequence analysis 311.3.3.4.Secondary structure 311.3.3.5.Details of a-helix structure 311.3.3.6.Tertiary structure 311.3.3.7.Denaturation (change inpH, temperature, 2metals, ethanol)11.3.4.Nuclei Acids and Protein Synthesis11.3.4.1.Pyrimidine and purine 311.3.4.2.Nucleosides and nucleotides 311.3.4.3.Formulae of pyrimidine and purine bases 311.3.4.4.Difference between ribose and 2-deoxyribose 311.3.4.5.Base combination CG and AT (hydrogen-bonding) 311.3.4.6.Difference between DNA and RNA 311.3.4.7.Difference between mRNA and tRNA 3 11.4.Enzymes11.4.2.1.General properties, active centers 311.4.2.2.Nomenclature, kinetics, coenzymes, function of ATP 312.Analytical chemistry12.1.Titrations12.1.2.acid-base12.1.2.1.Titration curve; pH (strong and weak acid) 212.1.2.2.Choice of indicators for acidimetry 212.1.3.Redox titration 312.2.Qualitative analysis12.2.2.Ions (Inorganic)12.2.2.1.Identification of Ag+, Ba z+, Cl-, SO42- 212.2.2.2.Identification of other anions and cations 3anic functional groups12.2.3.1.Lucas reagent (1-, 2-, 3-alcohols) 312.2.3.2.Iodoform reaction 312.2.3.3.Identification of primary, secondary, tertiary, 3quarternary amines in the laboratory12.3.Chromatographic methods of separation 3Part I Experimental partLevel 1: is assigned to the basic experimental activities which are supposed to be mastered by competitors very wellLevel 2: is assigned to the activities which are parts of school experimental exercises in developed countries and the authors of IChO tasks may incorporate them into the tasks without beingbounded to mention it in advanceLevel 3: is assigned to such activities which are not in the chemistry syllabus in the majority of participating countries and the authors are obliged to mention them in the set of preparatorytasksIf the organizer wants to apply a technique which is not mentioned in the above syllabus, this technique is set to level 3 automatically.1.Synthesis of inorganic and organic compounds1.1.Heating with burners and hotplates 1 1.2.Heating of liquids 1 1.3.Handling the work with inflammable substances and materials 1 1.4.Measuring of masses (analytical balance) 1 1.5.Measuring of volumes of liquids (measuring cylinder, pipette, 1burette)1.6.Preparation of solutions from a solid compound and solvent 1 1.7.Mixing and dilution of solutions 1 1.8.Mixing and stirring of liquids 1 ing mixer and magnetic stirrer 2 ing a dropping funnel 1 1.11.Syntheses in flat bottom vessels - general principles 1 1.12.Syntheses in round bottom vessels - general principles 1 1.13.Syntheses in a closed apparatus - general principles 1 1.1ing microscale equipment for synthesis 3 1.15.Apparatus for heating of reaction mixture under reflux 2 1.16.Apparatus for distillation of liquids at normal pressure 21.17.Apparatus for distillation of liquids at reduced pressure 2 1.18.Apparatus for steam distillation 3 1.19.Filtration through flat paper filter 1 1.20.Filtration through a folded paper filter 1 1.21.Handling a water vacuum pump 1 1.22.Filtration through a Buchner funnel 1 1.23.Suction through a glass filter 1 1.24.Washing of precipitates by decantation 1 1.25.Washing of precipitates on a filter 2 1.26.Drying of precipitates on a filter with appropriate solvents 2 1.27.Recrystallization of substances from aqueous solution 1 1.28.Recrystallization of substances from a known organic solvent 2 1.29.Practical choice of an appropriate solvent for recrystallization of a 3substance1.30.Drying of substances in a drying box 2 1.31.Drying of substances in a desiccator 2 1.32.Connecting and using of a gas washing bottle 21.33.Extraction with an inmiscible solvent 12.Identification of inorganic and organic compounds:general principles2.1.Test-tube reactions 1 2.2.Technique of reactions performed in a dot dish and on a filter paper 12.3.Group reactions of some cations and anions specified by the 2organizer2.4.Selective reactions of some cations and anions specified by the 2 organizer2.5.Specific reactions of some cations and anions specified by the organizer 3 2.6.Identification of elements by flame coloration (using a platinum 2wire/MgO rod, Co-glass)ing a hand spectroscope/Bunsen spectroscope 3 2.8.Melting point determination with Kofler or similar type of apparatus 3 2.9.Qualitative evidence of basic functional groups of organic 2substances specified by the organizer2.10.Exploitation of some specific reactions for identification of organic 3compounds (specified by the organizer)3.Determination of some inorganic and organic compounds:general principles3.1.Quantitative determinations using precipitation reactions 2 3.2.Igniting of a precipitate in a crucible 1 3.3.Quantitative volumetric determinations 1 3.4.Rules at titrating 1e of a pipetting ball 1 3.6.Preparation of a standard solution 2 3.7.Alkalimetric and acidimetric determinations 2 3.8.Color transitions of indicators at alkalimetric and acidimetric 2determinations3.9.Direct and indirect determinations (back titration) 3 3.10.Manganometric determinations 3 3.11.Iodometric determinations 3 3.12.Other types of determinations on basis of redox reactions 3 plexometric determinations 3 3.14.Color transitions of solutions at complexometric determinations 3 3.15.Volumetric determinations on basis of precipitation reactions 33.16.Thermometric titration 34.Special measurements and procedures4.1.Measuring with a pH-meter 2 4.2.Chromatography on thin layers 3 4.3.Column chromatography 3 4.4.Separation on ion exchanger 3 4.5.Measuring of UV-VIS absorbances with a spectral photometer 34.6.Performing of conductivity measurements 35.Evaluation of results5.1.Estimation of experimental errors (significant figures, plots scales) 1。
第三章-酸碱滴定法
共轭酸
conjugate acid
共轭碱 + H+
conjugate base proton
(一)理解质子酸碱理论： 酸碱共轭关系 酸碱反应的实质 酸碱的强度
（二） 酸碱反应的平衡常数 Equilibrium constant
酸的离解：Acid dissociation 水的自递：
HA H A
H2O H OH
Ka
HA HA
Kw HOH 1.00 1014(25o C)
Ka — 酸度常数，酸的离解常 数 Kw — 水的自递常数
碱的离解：Base dissociation 对共轭酸碱对 HA—A-
A H2O OH- HA
Kb
HAOH A
Kb — 碱度常数，碱的离解常 数
Ka Kb
K a1K a 2
[H ]2 Ka1[H ] [H ]2
d HA
[HA- ] c
Ka1Ka2
Ka1[H ] Ka1[H ] [H ]2
dA
[A2- ] c
K a1K a 2
K a1K a 2 Ka1[H ] [H ]2
ni
[H ]i Kaj
di n
j0 k
([H ]nk Kaj )
[HIn]
[HIn]
[H ]
因此可由颜色的变化判断[H+]的变化，确定滴定的终点。
理论变色范围：pKa1
0.1 [In ] 10 [HIn]
理论变色点：pKa 实际变色点：pT
分布系数
1.0
指
0.8 HIn
In
示
0.6
剂
0.4
变
0.2
色
0.0