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29. An introduction to A Level organic chemistry Formulas, Fn groups, Naming Functional groups and formulae Functional group: atom/group of atoms in an organic molecule that determines its characteristic chemical and physical properties Arenes: aromatic compounds that contain a benzene ring chemical properties Compound can undergo Electrophilic attack: is e- rich due to π system of delocalised e- Resistant to addition reactions: delocalised e- ring system makes benzene stable physical properties b.p 80 C: Benzene has id-id forces of attraction between the molecules Insoluble in water: non-polar hydrocarbons in arene (not energetically favourable for benzene to break many H bonds between water molecules to be soluble) Halogenoarenes: aromatic compounds containing halogen bonded to benzene ring chemical properties Prone to Electrophilic attack can take part in substitution reactions physical properties Chloro, broom, iodo benzene liquid at r.t with oily texture b.p. Increases down group: larger halogen = more e- = stronger id-id forces = more energy to separate insoluble in water: non-polar hydrocarbon ring Phenols: aromatic compounds containing a hydroxide bonded to benzene ring chemical properties acidic: O in -OH donates a lone pair into ring (more acidic than alcohols) = increased e- density in ring = more reactive = easier for H to be donated react with reactive metals (e.g. Na) to form phenoloxide ions and H gas physical properties White, crystallline solid disinfectant-like smell soluble in water: can form H bonds with water due to -OH group Acyl chlorides: carboxylic acid derivatives containing a chlorine atom, and an acyl group attached to C=O chemical properties colourless extremely reactive and readily takes part in substitution (Cl substituted ) fuming liquids with strong smell: react with water vapor in air Physical properties react violently with water (cannot determine its solubility with water ) Amines: compounds with -NH2 (primary), -NH (2 °) , or -N (3 ° ) amine group chemical properties basic compounds: due to lone pair of e- on nitrogen physical properties lone pair on N can form H bonds soluble in water: form H bond with water solubility ↓ as nonpolar hydrocarbon chain gets longer / molecule gets bigger fishy smell Amides: compounds containing amine group (-NH2) carbonyl group (C=O) amide group -CONH2 chemical properties less basic than amides: lone pair of e- on N is delocalised physical properties soluble in water: form H bonds with water solubility ↓ as nonpolar hydrocarbon chain gets longer / molecule gets bigger Amino Acids: building blocks of proteins, consisting amine group (-NH2) and carboxylic group (-COOH) chemical properties react with bases to form salts react with alcohols to form esters react with amines to form amides physical properties most are soluble in water but insoluble in organic solvents most have chiral centres, exhibit optical isomers Formulae of Organic Compounds Nomenclature of Compounds Naming organic compounds Identify longest C chain containing the functional group Identify fn group on the chain to determine the suffix or prefix on the compound Count along the carbon chain such that the functional group has the lowest number Add any side chains or lower priority functional groups as prefixes to the beginning of the name in alphabetic order Use the prefixes di-, tri- and tetra- if there are two or more identical functional groups or side chains Characteristic organic reactions Electrophilic substitution Electrophile: e- loving species they are e- deficient and acts as e- pair acceptor Substitution reactions: reactions replacing 1 atom / group by another Electrophilic substitution: group / atom replaced by an electrophile e.g. bromine electrophile attacks e- - rich benzene ring Addition-elimination (nucleophilic) nucleophilic addition of small molecule followed by elimination of small molecule includes hydrolysis reaction of alcohols to form esters reaction with ammonia and 1° amines to form amides e.g. Hydrolysis of acyl chlorides Hydrolysis - acyl chloride to carboxylic acid water molecule adds across C=O bond HCL eliminated Ester formation - acyl chlorides + alcohol Alcohol adds across the C=O bond HCl molecule is eliminated Amide formation - acyl chloride + 1° amines + conc ammonia amine or ammonia adds across C=O bond (lone pair on N attacks carbonyl C atom in acyl chloride) HCl eliminated Shapes of aromatic organic molecules Aromatic molecules consist of one or more rings with conjugated π systems Conjugated π systems arise from alternating double and single bonds in which the electrons are delocalised Shape of benzene and aromatic compounds - why are they more stable? Benzene and other aromatic compounds are planar and regular because each carbon atom is sp² hybridised. Each C forms three σ bonds in a trigonal planar arrangement with bond angles of 120°. The remaining unhybridised p orbital on each carbon overlaps sideways with neighbouring p orbitals to form a continuous, delocalised π system above and below the ring. Because the π electrons are delocalised over the whole ring, all the C–C bonds are identical and have intermediate character between a single and double bond. This is why benzene is unusually stable. Why are benzene more stable? delocalised π electrons above and below the ring Optical isomerism, Chirality and drug production Stereoisomers: same structural formula, diff arrangement in space (geometrical, optical) Optical 4 diff groups of / atoms central chiral carbon chiral molecules exist as 2 optical isomers / enantiomers non-superimposable mirror images same physical / chemical properties rotate in opposite directions in plane polarised light (1 clockwise 1 anticlockwise ) Similarities of enantiomers differences in enantiomers same physical and chemical properties differ from ability to rotate plane polarised light and biological activity nonsuperimposable mirror images Biological activity of enzymes enzymes are chiral proteins, bond to specific active site for biological response mirror image of enantiomer will not bind to same active site as it is not the same shape, no biological response Optical activity and Racemic mixtures reaction mixture is optically active if there is an uneven mixture of each enantiomer (e.g. 20% rotates clockwise, 80% rotates anticlockwise, net effect is plane of polarised light rotates anticlockwise) racemic mixture: equal amounts of enantiomers present in soln optically inactive as enantiomers cancel out each others effect, plane polarised light not changed the rotation of plane polarised light can be used to determine the identity of an optical isomer e.g. pass plane polarised light through a sample containing one of the two optical isomers of a single substance Depending on which isomer sample contains, the plane polarised light will be rotated clockwise / anti-clockwise clockwise rotation: R enantiomer anticlockwise rotation: S enantiomer No effect will be observed when the sample is a racemic mixture Chirality and Drug production most drugs to treat disease have 1+ chiral centres and can ∴exist as enantiomers diff in biological activity in enantiomers means difference in effectiveness as medicine drugs should be prepared so that only 1 optical isomer produced, to ↑ effectiveness Potential different biological activity of enantiomers e.g. drug naproxen treats pain from arthritis 1 enantiomer eases pain 1 enantiomer causes liver damage separate racemic mixture into 2 pure enantiomers due to difference in biological activities reduce side effects ↓ dosage by half, reduces production cost chiral catalysts to produce 1 pure optical isomer only small amount chiral catalysis needed + reused e.g. enzyme 30. Hydrocarbons - Arenes Reactions of arenes substitution halogenation nitration Friedel-Craft's alkylation Friedel-Craft's acylation other reaction Complete Oxidation Hydrogenation Electrophilic substitution electrophile: e- pair acceptor, attracted to delocalised e- substitution: 1+ H replaced by a fn group generating electrophile+ using catalyst Electrophilic attack on benzene ring (electrophile accepts 2 π e- , +ve charge remains) regenerating aromaticity by heterolytically cleavage of C-H bond (bonding pair foes into benzene π system) Addition reactions of arenes arenes undergo substitution due to delocalisation of e-, aromaticity restored by heterolytic cleavage of C-H bond in addition, aromaticity / stability not restored (e.g. hydrogenation), Hydrogenation of benzene is less exothermic than expected for three isolated C=C bonds, because the aromatic stabilisation of benzene is lost Halogenation (in the aromatic ring) reactants: Cl2 / Br2 (Cl+ / Br+ electrophile) , arene conditions: rt and pressure catalyst: anhydrous AlCl3 / AlBr3 (catalyst needed due to stability of benzene structure) formation: AlCl3 + Cl2 ⇒ AlCl4- + Cl+ reformation: H+ + AlCl4- ⇒ AlCl4 + HCl product: halogenoarenes / aryl halide In halogenation of Alkylarenes, e- donating alkyl group activates positions 2, 4 (as well as OH-, NH2). forms 2 products multiple substitutions when excess halogen used Halogenation (of alkylarenes) in side chain free radical substitution reaction reactants: halogen, boiling alkyl arene conditions: UV light if excess halogen: all H on alkyl side chain will be substitution by X atoms Nitration reactants: conc HNO3 (NO2+ electrophile), arene conditions: 20-60 ° C (higher = more NO2+ substituted) catalyst: conc H2SO4 formation: HNO3 + H2SO4 ⇒ NO2+ + 2HSO4- + H3O+ reformation: H+ + HSO4- ⇒ H2SO4 In nitration of Alkylarenes, e- donating alkyl group activates positions 2, 4 Friedel-Crafts alkylation substitution of alkyl chain reactant: chloroalkane (CH3CH2+ electrophile), arene condition: heat under reflux catalyst: anhydrous AlCl3 formation: AlCl3 + CH3CH2Cl ⇒ CH3CH2+ + AlCl4- reformation: AlCl4- + H+ ⇒ AlCl3 + HCl Friedel-Crafts acylation substitution of an acyl group (group containing carbonyl, C=O ) reactant: acyl chloride (CH3CH2CO+ electrophile) conditions: heat under reflux catalyst: anhydrous AlCl3 formation: AlCl3 + CH3CH2COCl ⇒ CH3CH2C=O+ + AlCl4- reformation: AlCl4- + H+ ⇒ AlCl3 + HCl Complete oxidation of side chains alkyl side-chains in alkyl arenes are oxidised to carboxylic acids when refluxed with alkaline KMnO4 and then acidified with dilute H2SO4 reactants: hot alkaline KMnO4, dilute H2SO4, alkyl arenes conditions: heat under reflux Hydrogenation addition reaction to form cyclohexane reactants: H2 gas conditions: heat (200 ° C at 30 atm ) catalyst: Pt/Ni Directing effects of substituents on arenes substituents: already on arene that direct substitution reactions to diff. ring positions E- withdrawing groups / substituents e- donating groups / substituents remove e- density from π system in benzene ring deactivating groups (slow attack by e+) directs e+ to positions 3, 5 e.g. COOH, X, NO2 donate e- density into π system of benzene ring activating groups (allow e+ to react faster) directs e+ to positions 2, 4, 6 e.g R, NH2, OH 31. Halogen compounds Halogenoarenes: arenes bonded to X atoms Producing halogenoarenes substitution reactions of arenes with chlorine or bromine in presence of anhydrous AlCl3 catalyst reactants: Cl2 / Br2 (Cl+ / Br+ electrophile) , arene conditions: rt and pressure catalyst: anhydrous AlCl3 / AlBr3 (catalyst needed due to stability of benzene structure) formation: AlCl3 + Cl2 ⇒ AlCl4- + Cl+ reformation: H+ + AlCl4- ⇒ AlCl4 + HCl product: halogenoarenes / aryl halide Substitution of benzene Substitution of methylbenzene substitution of 6 position only occurs in excess chlorine Reactivity of halogenoarenes Why are aryl halides less reactive than haloalkanes? C-H bond in aryl halides is stronger due to the partial overlap of lone pairs on halogen atom with the π system in the benzene ring C-H bond ∴ has a partial double bond character 32. Hydroxy compounds Reactions of alcohols Formation of esters reaction: addition-elimination (esterification) reactants: alcohols/phenols, acyl chlorides nucleophile: OH- (attacks e- deficient carbonyl (COCl) C ) COCl bond breaks, Cl is substituted, HCl fumes formed Why are esters formed from acyl chlorides rather than from C. acids? more effective to form esters from acyl chlorides acyl chlorides are more reactive (produce esters faster) acyl chloride reactions go to completion (more ester formed) Esterification using phenols additional reactants: base (e.g. NaOH) base: deprotonate phenol to form phenoxide ion phenoxide better nucleophile than phenol, attack on carbonyl C occurs more readily Phenol phenol: benzene ring with -OH group attached Production of Phenol From reaction of phenylamine with nitrous acid (HNO3) reactants: NaNO2, dilute acid (to form HNO2), phenylamine conditions: ice (under 10 ° C) step 1 and 2, heat step 3 forming nitrous acid NaNO2 + HCl ⇒ (ice) HNO2 + NaCl forming unstable diazonium salt forming phenol via thermal decomposition (due to instability) reactions of phenol Many reactions due to e- rich benzene ring and polar -OH group with bases with reactive metals with diazonium salts nitration bromination Acid-base reactions Acid-base reaction of phenols with base -OH: slightly acidic (weak acids), act as acid in acid-base reaction dissolve in alkaline soln forming phenoxide salt and water Acid-base reaction of molten phenols with reactive metals forms soluble phenoxide salt and H2 gas Reaction with diazonium ions diazonium ions very reactive due to -N2+ group acid-base reaction conditions: ice for cold diazonium ion added to phenoxide ion Reactions of the aromatic ring phenols react more readily with e+ than benzene due to one lone pair of e- on O in -OH overlaps with π bonding system, ↑ e- density of phenol’s benzene ring and making it more susceptible to electrophilic attack -OH activates ring, directs e+ to 2, 4, 6 positions Nitration of phenols electrophilic substitution reaction reactant: dilute HNO3, phenol when conc HNO3 used, product is 2, 4, 6- trinitrophenol conditions: rt milder conditions as phenol is more reactive Bromination of phenols electrophilic substitution reaction reactants: bromine water, phenol conditions: rt phenol decocolourises orange bromine soln to form 2, 4, 6 - tribromophenol (white ppt) as phenol is more reactive, no need for anhydrous AlBr3 catalyst, can react with bromine water Reactions of other phenolic compounds (contain phenol functional group, e,g, 1-naphthol) -OH group is also e- donating, activates benzene ring to electrophilic substitution reactions, e+ directed to 2, 4 positions (on phenol) C in position 6 shared by both rings, no H atom = no substitution can react in similar way as phenol Acidity of phenols Phenols are weak acids phenols react more readily with e+ than benzene due to one lone pair of e- on O in -OH overlaps with π bonding system, ↑ e- density of phenol’s benzene ring and making it more susceptible to electrophilic attack Phenol’s conjugate base is the phenoxide ion. -ve charge is delocalised over the entire ion as a lone pair on O overlaps with the ring’s delocalised π system, which reduces charge density on oxygen H⁺ ions are ∴ less strongly attracted to phenoxide ion, so phenol is less likely to reform Therefore, phenol is more likely to lose H⁺ and act as an acid Stability of conjugate base phenoxide more stable as -ve charge spread out, so phenol more likely undergo ionisation eqm shifts right, more phenol donate H+ (act as acid) Relative acidities of water, phenol, ethanol smaller pKa = stronger acid order of acidity explained by conjugate bases Delocalisation of charge density phenoxide (conjugate base of phenol): charge density of O is spread out over ion, O less available for bond formation with H+ ethoxide (conjugate base of ethanol): ethyl group is e- donating, donates e- density to O atom, O more available for bond formation with H+ hydroxide (conjugate base of water): charge density of O cannot become delocalised over a ring, OH- more readily accepts H+ than phenoxide no e- donating alkyl groups to O, less -ve O, O less readily accepts H+ compared to ethoxide Overall conjugate base more readily accepts H+ = stronger conjugate base = weaker acid strong acid eqm shifts right favouring dissociated ions and H+ 33. Carboxylic acids and derivatives Benzoic acid: C6H5COOH can be used to synthesize esters Carboxylic acids Production of benzoic acid formation of benzoic acid from Oxidation of alkylbenzenes alkylbenzene heated under reflux with hot alkaline KMnO4, then acidified with dilute acid to protonate carboxylate salt and form benzoic acid reactants: hot alkaline KMnO4 (oxidising agent), dilute acid (e.g. HCl), alkylbenzene purple Mn2+ turns colourless as reduced to Mn4+ brown ppt MnO2 formed conditions: heat under reflux Reactions of Carboxylic acids Reactions of C, acids to form acyl chlorides reactants PCl5 (s) PCl3 (l) + heat SOCl2 (l) Forming carboxylic acids from oxidation of 1 ° alcohols alcohol ⇒ aldehyde ⇒ c. acid Further oxidation of c. acids such as methanoic and ethanedioic acid methanoic acid (strong reducing agent) gets further oxidised to CO2 by warming with mild oxidising agents like Fehling’s or Tollen’s reagent Fehlings: Cu2+ reduced to Cu+, form red ppt Cu2O Tollens: Ag+ reduced to Ag using stronger oxidising agents like acidified KMnO4 or acidified K2Cr2O7 KMnO4: purple soln turns colourless as Mn7+ reduced to Mn2+ K2Cr2O7: orange soln turns green as the Cr6+ reduced to Cr3+ ions Ethanedioic acid gets further oxidised to CO2 Conditions: Strong oxidised agent - warm acidified KMnO4 needed Relative acidities of C. acids, Phenols, and alcohols C acids can lose H+ in aq soln to form carboxylate salts and water Acidities of C. acids longer C chain = weaker acid inductive effect ↑ -ve charge on COO- group More substituted Cl atoms = stronger acid Cl atoms withdraw e- density from the –COOH group, weakening the O–H bond and stabilise carboxylate ion (reducing the -ve charge density on it) The more stable the carboxylate ion, the less likely it is to attract H⁺ and reform the O–H bond Acidities of c. acids, phenols, alcohols acidities explained by strength of O-H bond and stability of conjugate bases of acids Strength of O-H bond carboxylic acids e- in O-H bond drawn towards C-O bond, e- in C-O bond drawn to C=O bond O-H bond weakened due to C=O withdrawing e- density from it for itself easier to act as acid and lose H+ from OH alcohols lack e- withdrawing C=O group, O-H bond not weakened harder to act as acid and lose H+ Stability of conjugate bases carboxylate ion (c base of carboxylic acid) charge density on O spread over ion because charge is delocalised on an electronegative carbonyl O atom O less available for bond formation with H+ to reform -COOH eqm shifts right, C base more stable than carboxylic acid alkoxide ion (c base of alcohol) alkyl is e- donating group, donates e- density to O atom O more available for bond formation with H+ ion to reform OH lack ability to delocalised charge density on ion, c bases less stable than alcohols, weaker acids than c. acid and phenols eqm lies left phenoxide ion (c base of phenol) charge density of O spread out over ion due to delocalisation of e- (stabilises ion) O less available for bond formation with H+ Phenoxide more stable than phenol Phenoxide less stable than carboxylate since delocalisation of charge density is on C atoms, not electrogenative O atoms eqm lies more right than alcohols, more left than c. acids ethanol is weakest e- donating methyl group strengthens O-H bond methyl donates -ve charge to -COO-, more likely to accept H+ Esters - Production Esters: organic compounds with -COO- functions group nice smelling Naming esters alcohol acyl chloride / carboxylic acid e.g. Producing esters from alcohols and carboxylic acids condensation / esterification reaction Producing esters from alcohols and acyl chlorides more effective: acyl chlorides more reactive(faster), and reactions go to completion (no eqm, max yield) Acyl Chlorides Acyl chlorides: compounds with COCl fn group Production of acyl chlorides Carboxylic acid with solid PCl5 liquid PCl3 + heat liquid SOCl2 Reactions of acyl chlorides addition-elimination: addition of small molecule across C=O, followed by elimination of small molecule acyl chlorides under addition-elimination reactions such as hydrolysis to form carboxylic acid Reaction with alcohols and phenols to form esters Reaction with ammonia and amines to form amides General mechanism for addition-elimination reactions addition of nucleophile across C=O bond elimination of a small molecule such as HCl or H20 lone pair on nucleophile carries out initial attack on carbonyl carbon this is followed by the elimination of an HCl molecule Hydrolysis of acyl chlorides forms carboxylic acid and HCl water (nucleophile) adds across C=O bond HCl eliminated Formation of esters from acyl chlorides esterification reaction reactants: alcohol/phenol, acyl chloride conditions: rt reaction with phenol is slower than alcohol, base such as NaOH used to speed up reaction (deprotonates phenol to form phenoxide, better nucleophile to carry out attack) alcohol /phenol (nucleophile) adds across C=O bond, HCl / NaCl eliminated Formation of amides from acyl chlorides condensation reaction: nucleophile adds to C=O, Cl- eliminated, HCl formed reactants: ammonia or 1°/2 ° amines, acyl chloride nucleophile: Nitrogen (has lone pair of e- ) HCl formed is immediately neutralised by a 2nd molecule of ammonia / amine in excess, forming ammonium salt (e.g. NH4Cl, CH3NH3Cl) Relative ease of hydrolysis of aryl chlorides from most readily broken / easily hydrolysed acyl chloride > alkyl chloride > aryl chloride trend explained by strength of C-Cl bond acyl chlorides - hydrolysed at rt R-COCl C bonded to Cl is also bonded to O both Cl and O are very electronegative, pulling e- away from C, leaving it very δ+ C-Cl bond is weakened nucleophilic attack is more rapid alkyl chloride - hydrolysed by refluxing with strong alkali nucleophile R-C-Cl C bonded to Cl attached to 1 electronegative atom (Cl), pulls e- away from C C is not very δ+ (e- deficient) C-Cl bond is stronger than in acyl chlorides aryl chlorides - hydrolysis will not occur C bonded to Cl is part of delocalised π bonding system of benzene ring one lone pair of e- on Cl overlaps with delocalised system C-Cl bond has some double bond character, becoming stronger 34. Nitrogen compounds Primary and secondary amines 1 ° amines: organic compounds with NH2 fn group attached to an alkyl / aryl group 2 ° amines: organic compounds with group attached to a alkyl /aryl groups Naming -amine: after alkyl prefix (e.g. methyl amine) amino- : if another suffix present or branched/complex amines (e.g. amino methane) Production of Amines 1 ° and 2 ° amines prepared form diff reactions 1 ° amines: reaction of haloalkanes with ammonia reduction of nitriles reduction of amides 2 ° amines: reaction of haloalkanes with 1 ° amine Forming 1 ° amines from haloalkanes with ammonia nucleophilic substitution reaction reactants: excess, hot ethanolic ammonia nucleophile: N in ammonia (replaces X) conditions: heat under pressure Forming 1 ° amine from reduction of nitrile reactants: nitrile vapour, H2 gas conditions: LiAlH4 in dry ether (reducing agent), or Ni catalyst Forming 1 ° / 2 ° amines from reduction of amides reactants: LiAlH4 in dry ether (reducing agent) type of amine depends on nature of amide Forming 2 ° amines from haloalkanes with 1 ° amine nucleophilic substitution reaction reactants: 1 ° amine in ethanol nucleophile: N in 1 ° amine (replaces X) conditions: heat under pressure, sealed tube Reactions of Amines Condensation reaction between Acyl chloride and ammonia or amine produces Amides Cl in acyl chlorides is electronegative, draws e- density from carbonyl C C is e- deficient, attacked by nucleophile like N in ammonia and amines C-Cl bond broken, amide formed reaction with amines ⇒ substituted amide reaction with ammonia ⇒ nonsubstituted amide Why is acyl chloride a more effective reactant than carboxylic acids in formation of amides? c acids less reactive than acyl chloride reaction with c acids dosent fo to completion Basicity of aq soln of Amines and ammonia N in ammonia and amines can accept proton H+, can ∴ act as bases in aq soln (when donating lone pair to form dative bonds) Strength of bases strength of amine depends on availability of lone pair of e- on N to form a dative covalent bond with H+ lone pair more readily available to form dative bond = stronger base positive inductive effect ↑ basicity: alkyl groups donate e- density to N, causing lone pair to become more available delocalisation ↓ basicity: aromatic rings cause lone pair to be delocalised into benzene ring, causing lone pair to be less available Phenylamine and Azo compounds Phenylamine: organic compound with benzene ring and amine fn group Production of phenylamine 3 step synthesis, followed by separation / purification Nitration (forming nitrobenzene) reactants: benzene, conc HNO3 catalyst: conc H2SO4 conditions: 25-60 ° C Reduction (forming phenylamine ion) conditions: hot tin (Sn) and conc HCl under reflux Deprotonation (forming phenylamine) reactants: NaOH, phenylamine ion separation/purification phenylamine separated from reaction mixture by steam distillation Reactions of Phenylamine Both benzene ring and NH2 can take part in chemical reactions bromination of phenylamine formation of diazonium salt Bromination of phenylamine to form 2, 4, 6- tribromophenylamine electrophilic substitution reaction electrophile: N, donate e- density into benzene ring, ↑ e- density in benzene ring activates it, more readily attacked by electrophiles reactants: aqueous bromine, phenylamine conditions: rt Formation of diazonium salt (salt containing N2+ group) reactants: nitrous acid/HNO2, HCl, phenylamine HNO2 formed in test tube with NaNO2 and dilute HCl conditions: below 10 ° C diazonium salt forms phenol upon warming with water Azo compounds Azo compounds: organic compounds with R-N=N=R / azo group often used as dyes Diazonium compounds: contain N2+ group Formation of Azo compounds from coupling reaction of benzene diazonium chloride salt with phenol multi-step process forming nitrous acid reactants: NaNO2, HCl conditions: test tube, under 10 °C / ice NaNO2 + HCl ⇒(ice) HNO2 + NaCl Diazotisation reactants: phenylamine, HNO2, dilute HCl conditions: below 10 ° C / ice (prevent thermal decomposition of diazonium ion to phenol, N and HCl) coupling reaction reactants: phenol, diazonium ion (acts as electrophile, sub into benzene ring of phenol) conditions: alkaline conditions (NaOH deprotonates phenol to phenoxide, more reactive to e+) Why are azo compounds very stable? The delocalised e- in π bonding systems extend across both benzene rings and the –N=N– bridge Other days formed from similar route e.g. formation of yellow dye from coupling reaction between benzene diazonium chloride and C6H5N(CH3)2 Amides Amide: organic compounds with CONR2 amide group non-substituted / 1 ° amide: N bonded to 2H atoms substituted / 2 ° amide: 1 or both H replaced by a hydrocarbon group Production of Amides Formation of Amides from acyl chlorides / c. acid with ammonia / amine condensation reaction: nucleophile adds to C=O, Cl- eliminated, HCl formed nucleophile: Nitrogen (has lone pair of e- ) conditions: rt HCl formed is immediately neutralised by a 2nd molecule of ammonia / amine in excess, forming ammonium salt (e.g. NH4Cl, CH3NH3Cl) Reactions of Amides Amide group can undergo reactions Hydrolysis with aqueous alkali or aqueous acid Reduction with LiAlH4 Hydrolysis of amides to form c. acid and ammonia/ 1 ° amine conditions: reflux with aq acid / alkali products differ depending with amide is substituted nonsubstituted ⇒ c. acid + ammonia substituted ⇒ c. acid + 1 ° amine when refluxed in excess acid⇒ ammonium salt formed base⇒ carboxylate ion formed (deprotonation) Reduction of amides to form amine conditions: LiAlH4 reducing agent nonsubstituted amide ⇒ 1 ° amine + H2O substituted amide ⇒ 2 ° amine + H2O Relative basicity of Amides and Amines lone pair of e- more readily available for dative bonding = stronger base more e- =stronger base amides - weaker base e- withdrawing O in C=O causes lone pair on N to delocalise into C=O group, removed e- density from N lone pair on N less readily available for bonding amine - stronger base e- donating alkyl groups ↑ e- density on N lone pair on N more readily available for bonding Amino Acids Amino acids: organic compounds with 2 fn groups basic amino -NH2 group acidic carboxylic acid -COOH group due to presence of basic and acidic group, they are amphoteric (act as acid and base) R group can be acidic, basic, or neutral Acid-base properties of amino acids + formation of Zwitterion amino acids can undergo most reactions of amines and c. acids, including acid-base reactions (amine + acid, C. acid + base) Amino acids can interact intramolecularly to form zwitterion Zwitterion: ion with both +ve (NH3+) and -ve (COO-) charge formed from amino acids in water due to charges, there are strong intermolecular forces of attraction between amino acids this makes amino acids soluble crystalline solids Zwitterions act as buffer soln acid added: pH ↓ COO- accepts H+ to reform COOH, zwitterion becomes +vely charged base added: pH ↑ NH3+ donates H+ to reform NH2, zwitterion becomes -vely charged Isoelectric point: point at which charge = 0 / zwitterion is neutral a pH level unique to each amino acid due to R group Formation of Peptide bonds NH2 group of one amino acid can react with COOH group of another amino acid to form dipeptide condensation reaction: H2O eliminated peptide bond / link formed dipeptides can undergo condensation reaction again to form tripeptide ( 3 amino acids) polypeptide: many amino acids join to form long chain of molecules proteins are polypeptides Electrophoresis Analytical separation technique, separates ions by placing them in an electric field Sample of amino acids placed between 2 oppositely charged electrodes +ve ions move to -ve electrode -ve ions move to +ve electrode Rate of ion movement depends on size of ions (larger = slower) charge of ions (highly charged = quicker) Electropherogram: bands on gel after electrophoresis each band = particular species Amino acids can be separated according to charge and mass they are colourless, sprayed with ninhydrin (brown/purple stain) to show where they have gone to Changes in charge of amino acid due to pH of solution isoelectric point: no overall charge, no movement of zwitterions pH > isoelectric point: -ve charge, move to +ve electrode pH < isoelectric point: +ve charge, move to -ve electrode -ve charged amino acid: NH3+ donated H+, NH2 and COO- left +ve charged amino acid: COO- accepted H+, NH3+ and COOH left 35. Polymerisation Condensation Polymerisation - Forming polymers Forming polymers such as polyesters, polyamides, proteins Formation of polyesters addition polymerisation: monomers with C=C bonds join to form polymers condensation polymerisation: Small molecule is lost when monomers join together to form polyester polyesters have ester links Monomers for polyesters OH on dicarboxylic acid and H of diol expelled as H2O to form polyester diol (2 -OH) + dicarboxylic acid (2 -COOH) 2 hydroxy carboxylic acids (OH and COOH fn group) Formation of polyamides condensation polymerisation polyamides have peptide links Monomers for polyamides H on diamide and OH on dicarboxylic acid / Cl on dichloride expelled as H2O / HCl as polyamide forms diamide (2 -NH2) + dicarboxylic acid diamide + dichloride (2 -COCl) 2 aminocarboxylic acids (OH and COOH fn group) Making proteins/polypeptides from amino acid monomers (aminocarboxylic acid) amine group (-NH2) and carboxyl group (-COOH) of an amino acid polymerise with another amino acid forms peptide links proteins can be broken into its constituent amino acids through hydrolysis You can deduce the repeat units of a condensation polymer by identifying the linking between monomers chain of C: addition polymer ester link: polyester peptide link: polyamide You can identify monomers from small molecule expelled H2O: c acid H: amine Cl: dioyl chloride Predicting type of polymerisation Identifying type of polymerisation by looking at functional groups Addition polymerisation monomer contains C=C bond double bond opens up to add monomers to either side of starting polymer forms polyalkenes co-polymer: 2+ monomers used to make 1 repeating unit Condensation polymerisation makes polyamides and polyesters summary: Identifying type of polymerisation by considering structure of polymer backbone Addition polymerisation no fn groups on polymer backbone, usually chain of C atoms sidechains might branch off from backbone (e.g. benzene rings, nitrile groups (CN), halogens Condensation polymerisation backbone of polyesters contain ester links (-COO-) backbone of polyamides contain peptide links (-CONH-) Degradability of Polymers Polyalkenes and biodegradability polyalkenes are nonpolar and saturated, making them nonbiodegradable and chemically inert instead, they can be melted and recycled for new uses The energy released from burning can be used to generate electricity Burning plastics in oxygen releases carbon dioxide and water (complete combustion) which can contribute to global warming Photodegradation of polymers some polymers are biodegradable due to their ability to breakdown using light C=O groups along polymer chains absorb UV light this weakens C=O areas of polymers and breaks them down into smaller molecules e.g for polyesters and polyamides Disadvantages of photodegradability weaker polymers UV light not available (e.g. in landfills) Biodegrading polyesters and polyamides via hydrolysis polyesters and polyamides can be broken down by hydrolysis (advantage) hydrolysis: breakdown of molecules using water acid hydrolysis: acid catalyst used alkaline hydrolysis: alkaline catalyst used heating with catalyst breaks polymer Hydrolysis of polyamides acid hydrolysis: breaks polymer into di carboxylic acid and ammonium ions alkali hydrolysis breaks polymer into its sodium salts (e.g. dicarboxylic acid salt and diamines) Hydrolysis of polyesters acid hydrolysis: diol + dicarboxylic acid alkali hydro lists: diol + dicarboxylic acid salt 36. Organic synthesis Elucidating organic molecules - fn groups, properties, reactions Fn groups in AS required as well as: Production of fn groups benzoic acids acyl chlorides amides Producing benzoic acid reactants: methylbenzene oxidation: reflux with hot alkaline KMnO4 to form potassium benzoate protonation with dilute HCl to form benzoic acid Producing acyl chlorides reactants: c. acid substitution reaction: -OH replaced by Cl Producing amides condensation reaction reactants: acyl chloride, NH3 (nonsubstituted amide) / methyl amine (substituted amide) conditions: rt Reactions of functional groups Electrophilic substitution reactions of benzene reaction electrophile halogenation X+ nitration NO2+ alkylation R+ acylation RCO+ Hydrogenation of benzene addition reaction Esterification of phenol more efficient with acyl chloride than carboxylic acid Acid-base reactions of phenol phenol + base ⇒ soluble salt + water Nitration of phenol Bromination of phenol Multi-step synthetic routes Aliphatic reactions Aromatic reactions Analysis 37. Analytical techniques Thin- Layer Chromatography (TLC) Separate small samples 2 phases: stationary and mobile phase Stationary phase thin metal sheet coated in Al2O3, or SiO2 solutes adsorb onto surface and travel thru plate Mobile phase flows over stationary phase polar (water or alcohol) or nonpolar (alkanes), any liquid solvent or gas solvent carries components investigated in coloured components: investigated under UV light using ninhydrin Conducting a TLC analysis prep beaker with small amount of solvent on TLC plate, draw baseline in pencil place spot of reference compound on the left, then a spot of sample on right of baseline and air dry reserve allows identification of compounds in sample put TLC plate inside beaker with solvent - make sure pencil line above solvent, place lid to cover beaker as solvent reaches top, remove plate and draw another pencil line where solvent reached (solvent front) to use to calculate Rf Rf values The extent to which components are separated depends on solubility of each component in the mobile phase and interaction between each component and the stationary phase less polar components travel further up ⇒ larger Rf ⇒ more soluble in mobile phase more polar components do not travel far up ⇒ more attracted to polar stationary phase Gas / Liquid chromatography Analysing bases, volatile liquids, solids in vapour form Stationary phase nonpolar, non-volatile liquid applied to the inner walls of a capillary column mobile phase unreactive carrier gas noble, or inert diatomic e.g. He, N2, Ar Retention time: time taken for sample molecule to travel through the column from time inserted to time detected often recorded on chromatogram each peak = a volatile compound in the analysis sample. each peak has its own rt rt compared with data book values to identify unknown molecules longer rt: nonpolar components, attractiveness to nonpolar liquid in stationary phase shorter rt: polar components, interact with carrier gas Relative concentration of each component = area under each peak Area under peak = ½ base x height peaks roughly take shape of Δ % composition of a particular molecule in a mixture Carbon-13 NMR spectroscopy carbon-13 NMR : analytical tool used to analyse samples and determine the structure of substances Each Carbon environment gives a peak solvent used to dissolve samples for 13C-NMR : CDCl3 (solvent peak around 70 ppm) all 13C-NMR spectra measured relative to TMS / tetramethylsilane ( 0 ppm) predict the number of carbon environments refers to a specific c atom and the combination of atoms, bonds, fn groups attached each unique c environment produces a peak in 13C - NMR if there is a line of symmetry through the molecule, they belong to same environment and product a single peak e.g. predict no. peaks in 13C-NMR spectrum of 1,3-dihydroxybenzene 4 environments = 4 peaks predict each carbon’s chemical shift this is the frequency of an atomic nucleus relative to TMS reference compound measured in ppm example- 13C-NMR spectrum for propanone both CH3 groups are in same environment 2 environments = 2 peaks C=O peak over 200 C-H peaks 0-50 Proton (1H) NMR spectroscopy Technique used to determine structure of molecules paired with other techniques like Mass spec Magnetic field strengths of protons in organic compounds measured and recorded on H NMR spectrum all samples measured against reference compound TMS / Tetramethylsilane single sharp peak at 0 ppm Sample peaks plotted as a ‘shift’ away from this reference peak gives rise to ‘chemical shift’ values for protons on the sample compound (measured in ppm) Features of NMR spectrum intensity of peak against chemical shift area under peak: no. protons in particular environment height: intensity / absorption from protons Molecular / chemical environments diff. arrangements of H atoms have diff environments (identical / symmetry = same environment) no. environments = no. diff chemical shifts / peaks e.g. How many different 1H chemical environments occur in 2-methylpropane? 2 1H chemical environments 2 peaks on 1H NMR spectrum Chemical shift values for H molecular environments symmetrical H = same environment 1 ppm → Alkane 2 ppm → Next to C=O 7 ppm → Benzene ring 9–10 ppm → Aldehyde 10–12 ppm → Carboxylic acid Low resolution 1H NMR peaks on a low resolution NMR spectrum refer to the molecular environments of an organic compound High resolution 1H NMR number of peaks a signal splits into = n + 1 n = number of H on adjacent C atom n+1 splitting patterns Common pairs of splitting patterns TMS and deuterated solvents TMS gives sharp peak at 0 on NMR spectrum why is TMS an ideal reference chemical? it is inert and volatile it reduces undesirable chemical reactions with compound analyses it mixes well with most organic compounds Deuterated solvents in 1H NMR CDCl3 used as a solvent, no peak why is a solvent needed for samples in 1H NMR? dissolving samples in solvent help separate molecules and prevent them from interacting what must the solvent do? be a good solvent for organic molecules not contain any H atoms, does not interfere with NMR signals examples of non-deuterated solvents Carbon tetrachloride, CCl4: This solvent does not contain hydrogen, so it does not produce 1H NMR signals. It is suitable for 1H NMR but does not dissolve all molecules well. examples of deuterated solvents Deuterated solvents are often used in 1H NMR because deuterium (²H) is an isotope of H whose nuclei absorb in a different region from protons, so it gives no signal in a ¹H NMR spectrum Deuterochloroform / Chloroform-d, CDCl3: preferred, contains deuterium (2H) instead of H, does not interfere with the H NMR Deuterium oxide / Heavy water, D2O: deuterium atoms exchange reversibly with the H in the -OH and -NH, signals identified in NMR Identifying -OH and -NH signals Protons in -OH (hydroxyl) and -NH (amine) groups give singlet peaks in ¹H NMR but these signals can be tricky: peaks are broad or sometimes fall outside normal chemical shift ranges H in these groups exchanges quickly with protons from water or acids, so only one peak appears Their chemical shift ranges may overlap with other types of protons To identify these groups more clearly, proton exchange with deuterium oxide (D2O) is used: The deuterium atoms in D2O exchange reversibly with the protons in the -OH or -NH groups -OH + D2O ⇌ -OD + HOD -NH-CO- + D2O ⇌ -ND-CO- + HOD Since deuterium does not absorb in the same region as protons in the NMR spectrum, the signal for -OH or -NH disappears after D2O is added This confirms the presence of -OH or -NH groups in the molecule If peak disappears after D2O, it is due to the exchange of a proton from an -OH or -NH group
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AP U.S. Government Midterm Study Guide UNIT 1: FOUNDATIONS OF AMERICAN DEMOCRACY Topic 1.1: Ideals of Democracy Required Foundational Document: Declaration of Independence 1. Enlightenment Philosophical Foundations John Locke (Second Treatise of Civil Government): Natural law dictates that all individuals are born free and equal with natural rights (life, liberty, property). Government authority derives solely from the consent of the governed. If a government breaks the social contract or violates natural rights, citizens are obligated to alter or abolish it. Thomas Hobbes (Leviathan): Believed human nature in a state of nature is "solitary, poor, nasty, brutish, and short," resulting in anarchy. People surrender freedoms in a social contract to an absolute sovereign (Leviathan) in exchange for peace and social order. Jean-Jacques Rousseau (The Social Contract): Envisioned popular sovereignty—the people as the ultimate ruling authority—where free individuals abandon certain natural freedoms to form a body politic committed to the general good. Baron de Montesquieu (The Spirit of the Laws): Championed a republican government with defined, limited powers and advocated for the separation of powers into executive, legislative, and judicial branches to prevent tyranny. 2. Core Democratic Ideals & Foundational Documents Key Ideals: Natural rights, popular sovereignty, social contract, republicanism (electing representatives for a limited term to make laws in the public interest), and limited government (government restricted by law, checks, and balances). Declaration of Independence (1776): Authored primarily by Thomas Jefferson. Drafted by a committee of five (Jefferson, Adams, Franklin, Sherman, Livingston). Provided a moral and legal justification for rebellion against King George III by arguing that abusive taxation and British tyranny violated natural rights and the social contract. U.S. Constitution (1787): Codified ideals of self-government, checks and balances, separation of powers, and majority rule balanced with minority rights into a functional blueprint for a representative republic. Topic 1.2: Types of Democracy Model of Democracy Core Definition & Characteristics Historical & Contemporary Examples Participatory Democracy Emphasizes broad, direct participation of citizens in politics and civil society. Citizens vote directly on laws rather than relying exclusively on elected representatives. Town hall meetings, state/local ballot initiatives (citizens place measures on ballot), referendums (citizens vote to approve/defeat legislative acts). Pluralist Democracy Non-governmental interest groups activate to compete for political influence in a "marketplace of ideas." Policymaking is a result of bargaining, negotiation, and compromise among diverse interest groups. Interest groups testifying at congressional hearings, filing lawsuits, lobbying (e.g., NRA, NAACP, NOW, AFL-CIO, environmental groups). Elite Democracy Elected representatives act as trustees for voters; power is concentrated among educated, wealthy, or well-resourced individuals who possess the expertise to govern wisely. The Electoral College choosing the President, lifetime appointments of federal judges, original election of U.S. Senators by state legislatures. Topic 1.3: Government Power and Individual Rights Required Foundational Documents: Federalist No. 10, Brutus No. 1 1. Federalist vs. Anti-Federalist Debate Federalists (Hamilton, Madison, Jay): Supported ratifying the 1787 Constitution. Favored a strong central national government to maintain order, national security, and economic stability. Argued that a large, extended republic would protect individual rights by taming factions. Anti-Federalists (Patrick Henry, George Mason, Robert Yates): Opposed the new Constitution. Feared a strong national executive would replicate a British monarch and warned that the "Necessary and Proper" and "Supremacy" clauses gave the national government unchecked power, threatening state sovereignty and individual rights. Demanded a Bill of Rights. 2. Required Document Comparison Feature Federalist No. 10 (James Madison) Brutus No. 1 (Anti-Federalist Pseudonym) Central Argument A large, diverse representative republic is the best mechanism to control the "mischiefs of faction." A large, extended republic will destroy state sovereignty, erode individual liberty, and result in tyranny. View on Factions Factions are inevitable due to human nature. They cannot be eliminated without destroying liberty. Therefore, their effects must be controlled through a large republic where competing interest groups neutralize one another. In a large country, citizens' interests are too diverse ("clashing of opinions"), leading to constant legislative gridlock or government overreach to maintain order. Representation A large pool of voters ensures qualified, virtuous leaders are elected as representatives (trustees), insulating government from rash popular passion. Representatives in a large nation will be distant, unacquainted with local constituent needs, unaccountable, and prone to abuse their elevated power. Topic 1.4: Challenges of the Articles of Confederation Required Foundational Document: Articles of Confederation 1. Structure of Government Under the Articles (1781–1789) Unicameral Confederation Congress; each state possessed exactly one vote regardless of size or population. No executive branch to enforce national laws; no national judicial system to resolve disputes between states. Passing national legislation required approval by 9 of 13 states; amending the Articles required unanimous consent (13 of 13 states). 2. Key Weaknesses & Consequences Provision / Limitation Systemic Weakness & Impact No Direct Power to Tax Congress could only request funds from states. The national government faced immense Revolutionary War debt and could not pay foreign creditors or military veterans. No Power to Raise/Maintain a Standing Army The federal government relied on state militias and could not effectively secure national borders or suppress internal civil unrest. Inability to Regulate Interstate Commerce States imposed tariffs on goods from other states, issued conflicting paper currencies, and engaged in economic trade wars, paralyzing economic growth. Unanimity Amendment Requirement A single state (e.g., Rhode Island) could veto necessary tax reforms or constitutional adjustments, creating legislative paralysis. 3. Catalyst for Change: Shays' Rebellion (1786–1787) Impoverished Revolutionary War veteran Daniel Shays led an armed insurrection of Massachusetts farmers facing mortgage foreclosures and high state taxes. The insurgents forcibly closed debt courts and attacked the Springfield federal arsenal. Because the national government lacked funds and an army, Massachusetts had to rely on a privately funded militia to suppress the rebellion. Significance: Exposed the dangerous weakness of the central government under the Articles of Confederation, convincing national leaders (such as Washington, Madison, and Hamilton) to convene the Philadelphia Convention in May 1787. Topic 1.5: Ratification of the U.S. Constitution Required Foundational Document: The Constitution of the United States 1. Constitutional Compromises Virginia Plan vs. New Jersey Plan: Virginia Plan (James Madison): Bicameral legislature with representation in both houses based on population; favored large states. New Jersey Plan (William Paterson): Unicameral legislature with equal representation (one state, one vote); preserved state sovereignty for small states. Great (Connecticut) Compromise: Authored by Roger Sherman. Created a bicameral Congress consisting of: House of Representatives: Apportioned by state population (appeased large states); directly elected by voters. Senate: Equal representation (2 senators per state, appeased small states); originally chosen by state legislatures. Three-Fifths Compromise: Agreed that three out of every five enslaved persons would count toward a state's total population for House representation and federal direct tax assessments. Slave Trade Compromise: Prohibited Congress from banning the international slave trade for 20 years after ratification (until 1808) and included a fugitive slave extradition clause. Electoral College Compromise: Reconciled debates over whether Congress or direct popular vote should select the president. Each state chooses electors equal to its total congressional representation (House + Senate) to elect the executive. Commerce Compromise: Allowed Congress to regulate interstate and foreign commerce and levy tariffs on imports, but prohibited taxing exports. 2. The Constitutional Framework (Articles I–VII) Article I: Legislative Branch (Structure, Enumerated Powers, Necessary & Proper Clause). Article II: Executive Branch (Qualifications, Commander-in-Chief, Executive Duties). Article III: Judicial Branch (Supreme Court and Inferior Federal Courts). Article IV: Relations Among States (Full Faith and Credit, Privileges and Immunities, Extradition). Article V: Amendment Process (Two-stage process requiring 2/3 vote in Congress/Conventions to propose, 3/4 state legislatures/conventions to ratify). Article VI: National Supremacy Clause (Constitution and federal laws are supreme law of the land). Article VII: Ratification procedure (Required approval by 9 of 13 state conventions). 3. Modern Policy Debates Over Central Power Individual Rights vs. National Security: USA PATRIOT Act (2001) expanded executive surveillance authority after 9/11, sparking Fourth Amendment privacy concerns. The USA FREEDOM Act (2015) curtailed bulk phone metadata collection. Education Policy: Federal legislation such as No Child Left Behind (2002) and Every Student Succeeds Act (2015) reflect ongoing tension between federal standard-setting and state control under the 10th Amendment. Topic 1.6: Principles of American Government Required Foundational Document: Federalist No. 51 1. Foundational Theory: Federalist No. 51 (James Madison) "Ambition must be made to counteract ambition": Human nature is prone to self-interest. To prevent tyranny, government authority must be divided among distinct branches, giving each branch the constitutional means and motives to check the others. Division of Legislative Power: Because legislative power naturally predominates in a republic, Madison argued for dividing Congress into two branches (House and Senate) with different election modes and responsibilities. Double Security of Federalism: Power is first divided between two distinct governments (federal and state) and then subdivided among three branches within each, providing multiple layers of protection for individual rights. 2. Practical Checks and Balances System Branch Possessing Power Constitutional Check Over Legislative Constitutional Check Over Executive Constitutional Check Over Judicial Legislative (Congress) Bicameralism (House and Senate check each other). Overriding vetoes (2/3 vote), power of the purse, impeachment (House) and trial/removal (Senate), Senate advice and consent on appointments/treaties. Senate confirmation of judges, impeachment/removal of federal judges, altering court size/jurisdiction, proposing constitutional amendments. Executive (President) Vetoing legislation, calling special sessions, pocket vetoes. Internal administrative oversight. Nominating federal judges, power to grant pardons and reprieves. Judicial (Courts) Declaring laws passed by Congress unconstitutional (Judicial Review). Declaring executive actions or orders unconstitutional (Judicial Review). Chief Justice presides over presidential impeachment trials in the Senate. Topic 1.7: Relationship Between the States and Federal Government 1. Constitutional Allocation of Powers Exclusive (Delegated/Expressed) Powers: Granted solely to the federal government (e.g., declaring war, coining money, regulating interstate commerce, conducting foreign diplomacy, defining naturalization). Reserved Powers (10th Amendment): Powers not delegated to the federal government nor prohibited to the states are reserved to the states or the people (e.g., police powers—regulating health, safety, welfare, morals; operating schools; issuing licenses). Concurrent Powers: Powers shared by both national and state governments (e.g., levying taxes, enforcing laws, establishing court systems, borrowing money). 2. Fiscal Federalism & Financial Intergovernmental Relations Categorical Grants: Federal grants given to states for specific, narrowly defined purposes with strict requirements ("strings attached"). Gives the federal government significant leverage over state policy (e.g., National Minimum Drinking Age Act of 1984 tied highway funding to raising drinking age to 21, upheld in South Dakota v. Dole). Block Grants: Federal funds provided to states for broadly defined policy areas (e.g., community development, social services) with minimal federal conditions, granting states significant discretion (advocated during Devolution). Federal Mandates: Directives issued by the federal government requiring states to comply with national standards: Funded Mandates: Accompanied by federal financial aid. Unfunded Mandates: Requirements imposed without federal funding, forcing states to absorb compliance costs (e.g., Americans with Disabilities Act [ADA] of 1990, Clean Air Act Amendments). Devolution: The political movement to transfer power and administration from the federal government back to state and local governments (popularized during the Reagan administration and the 104th Congress, leading to the Personal Responsibility and Work Opportunity Reconciliation Act of 1996). Topic 1.8: Constitutional Interpretations of Federalism Required Supreme Court Cases: McCulloch v. Maryland (1819), United States v. Lopez (1995) Required SCOTUS Cases Comparison Case Name McCulloch v. Maryland (1819) United States v. Lopez (1995) Constitutional Issue Necessary and Proper Clause (Art. I, Sec. 8); Supremacy Clause (Art. VI). Commerce Clause (Art. I, Sec. 8); 10th Amendment Reserved Powers. Essential Facts Congress chartered the Second Bank of the U.S. The state of Maryland levied a tax on the bank to drive it out of state. Cashier James McCulloch refused to pay. Alfonso Lopez carried a concealed firearm into a Texas high school and was charged under the federal Gun-Free School Zones Act of 1990. Holding / Decision Unanimous (6–0) for McCulloch. Congress has the authority to charter a bank; states cannot tax federal institutions. Majority (5–4) for Lopez. The Gun-Free School Zones Act is unconstitutional because gun possession in a school zone does not substantially affect interstate commerce. Constitutional Impact Established national supremacy and solidified implied powers under the Necessary and Proper Clause ("The power to tax involves the power to destroy"). Expanded federal authority. Marked a major shift toward Devolution and state rights. Restricted Congress's reliance on the Commerce Clause, re-establishing limits on federal power over local policing/education. Topic 1.9: Federalism in Action 1. Impact on Policymaking Multiple Access Points: Stakeholders, interest groups, and citizens can influence policy across multiple levels (local, state, national) and branches (executive, legislative, judicial). If a group fails at the federal level, it can pursue initiatives at the state level. Laboratories of Democracy: States can experiment with novel social and economic policies without risking the entire nation (e.g., marijuana legalization, environmental regulations, healthcare reform models). 2. Federal-State Policy Conflicts Environmental Policy: Federal laws like the Clean Air Act and international agreements (e.g., Paris Agreement) face friction when federal rules conflict with state industrial standards or state-led cap-and-trade initiatives. Marijuana Legalization: While cannabis remains a Schedule I illegal drug under federal law (Controlled Substances Act of 1970, upheld in Gonzales v. Raich), numerous states have legalized medical and recreational marijuana through direct ballot initiatives. Federal enforcement relies heavily on executive department discretion. UNIT 2: INTERACTIONS AMONG BRANCHES (CONGRESSIONAL BRANCH) Topic 2.1: Congress: Senate and House of Representatives Required Foundational Document: U.S. Constitution (Article I) Institutional Differences Between Houses Feature / Institutional Metric House of Representatives U.S. Senate Membership Size 435 members (apportioned by population via Reapportionment Act of 1929). 100 members (2 per state). Term Length & Cycles 2-year terms; entire House up for election every 2 years. 6-year terms; staggered elections (1/3 of Senate up every 2 years; continuous body). Constituency Local single-member congressional districts (~700,000+ constituents). State at-large voters (broad, diverse constituency). Qualifications At least 25 years old, U.S. citizen for 7 years, resident of state represented. At least 30 years old, U.S. citizen for 9 years, resident of state represented. Exclusive Powers Originates all revenue/tax bills, initiates impeachment charges, selects President if Electoral College ties. Advice and consent on presidential nominations and foreign treaties (2/3 vote), conducts impeachment trials (2/3 vote to convict/remove). Debate & Debate Structure Highly structured, formal, centralized. Strict time limits on debate controlled by the Rules Committee. Less formal, decentralized. Unlimited debate permitted (filibusters allowed unless stopped by cloture). Constitutional Amendment Impact 14th Amendment protection; original popular election preserved. 17th Amendment (1913): Shifted election of Senators from state legislatures to direct popular vote. Powers of Congress (Article I, Section 8) Power of the Purse: Authority to levy taxes, collect revenue, coin money, and pass statutory appropriations funding federal programs. Regulating Commerce: Power to regulate international and interstate trade (Commerce Clause). Foreign & Military Powers: Exclusive power to declare war, raise and fund armies/navies, regulate military draft, and pass the War Powers Act of 1973 (requiring president to notify Congress within 48 hours of deploying troops and withdraw after 60 days unless authorized). Implied Powers: Authority grounded in the Necessary and Proper Clause to enact laws and execute delegated powers. Topic 2.2: Structures, Powers, and Functions of Congress 1. Congressional Leadership System Speaker of the House: Only House leadership position mandated by Constitution. Elected by majority party; presides over House, assigns bills to committees, recognizes speakers, and influences legislative agenda. Floor Leaders (Majority/Minority Leaders): Lead debate for their respective parties, guide strategy, and serve as national party spokespersons. Whips (Majority/Minority Whips): Enforce party discipline, tally prospective votes, and persuade members to vote along party lines. President of the Senate: The Vice President of the U.S.; non-voting presiding officer except to break tie votes. President Pro Tempore: Senior member of Senate majority party; presides over Senate in VP's absence. Senate Majority Leader: Most powerful figure in the Senate. Sets legislative calendar, controls floor debate, and determines which bills reach the floor. 2. The Committee System Committee Type Primary Role & Function Standing Committees Permanent panels handling specific policy areas (e.g., House Ways and Means, Senate Judiciary, Armed Services). Conduct hearings, mark up bills, and perform legislative oversight. Select / Special Committees Temporary committees established for a specific, limited investigation or study (e.g., Select Committee on Benghazi, Watergate). Joint Committees Panels containing members from both House and Senate to coordinate routine administrative issues or long-term studies (e.g., Joint Committee on Taxation). Conference Committees Temporary compromise panels formed to reconcile differing versions of House and Senate bills into a single, identical draft before sending to the president. 3. Chamber-Specific Rules & Procedures House Rules Committee: Acts as the "traffic cop" of the House. Determines rules for floor debate (time limits, open vs. closed amendment rules) and schedules bills. Committee of the Whole (House): Procedure designed to relax House rules, speed up debate, and require a reduced quorum of only 100 members. Discharge Petition (House): A petition signed by a simple majority (218 members) that forces a stalled bill out of a reluctant committee onto the House floor for a vote. Filibuster & Cloture (Senate): Tactical delay weapon using unlimited debate to block action on a bill or nomination. Stopped only by a Cloture Motion (Rule 22) requiring a 3/5 supermajority (60 votes). Holds & Unanimous Consent (Senate): Hold: An informal request by a senator to delay or prevent a bill or nomination from reaching the floor. Unanimous Consent Agreement: Set procedure rules to speed up Senate business by bypassing formal rules with unanimous approval. 4. The Federal Budgetary Process Mandatory Spending: Spending required by existing law for entitlement programs (e.g., Social Security, Medicare, Medicaid). Consumes over 60% of federal budget. Discretionary Spending: Spending that congressional committees debate and alter annually (e.g., defense spending, education, transportation). Deficit & National Debt: A budget deficit occurs when federal expenditures exceed federal tax revenue in a fiscal year. Accumulated annual deficits constitute the overall National Debt. Pork-Barrel Spending & Earmarks: Congressional add-ons to bills that direct federal funding to specific local projects in a member's district. Often attached to broader Omnibus ("Christmas Tree") Bills. Logrolling: The practice of trading votes among members of Congress to secure passage of individual legislative priorities. Topic 2.3: Congressional Behavior Required Supreme Court Cases: Baker v. Carr (1962), Shaw v. Reno (1993) 1. Member Voting Models Delegate Model: Lawmakers vote strictly according to the expressed desires of their constituents. Trustee Model: Lawmakers use their independent judgment, expertise, and moral conscience to make policy decisions, even if it contradicts constituent desires. Politico Model: A hybrid approach where lawmakers vote as delegates on high-profile issues with clear constituent consensus, but act as trustees on complex, low-visibility issues. 2. Gerrymandering & Redistricting Dynamics Reapportionment & Redistricting: Every 10 years following the U.S. Census, seats in the House are reapportioned. State legislatures redraw congressional district boundaries. Partisan Gerrymandering: Drawing district lines to give one political party an unfair advantage, creating a large number of "safe seats" (districts where a party consistently wins by 55%+). This practice leads to increased political polarization, as members fear primary challenges from ideologically extreme opponents ("getting primaried"). 3. Required SCOTUS Redistricting Cases Case Name Baker v. Carr (1962) Shaw v. Reno (1993) Constitutional Issue 14th Amendment Equal Protection Clause (Urban vs. Rural Apportionment). 14th Amendment Equal Protection Clause (Racial Gerrymandering). Essential Facts Tennessee failed to redraw its state legislative districts for over 60 years. Population growth in urban areas created massive population disparities between rural and urban districts, diluting urban votes. North Carolina created a wildly irregular, 160-mile majority-black district ("I-85 District") to comply with Justice Department demands for additional minority representation. White voters challenged the map. Holding / Decision 6–2 for Baker. Apportionment and redistricting claims are justiciable in federal court (not merely political questions). 5–4 for Shaw. Redistricting plans that cannot be explained on grounds other than race are subject to strict scrutiny under the Equal Protection Clause. Constitutional Impact Established the landmark "One Person, One Vote" principle, requiring legislative districts within a state to contain roughly equal populations. Prohibited race from being the predominant factor in drawing district lines, restricting racial gerrymandering even if intended to benefit minority representation. 4. Divided Government & Institutional Gridlock Divided Government: Occurs when one political party controls the White House and the opposing party controls one or both houses of Congress. Impacts: Causes policy gridlock, increases legislative stalemates, slows down statutory confirmation of presidential appointments, and heightens conflict during Supreme Court judicial nominations (e.g., blocking "lame duck" judicial nominees).
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Prunus serotina lecture notes
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PRONE ON ELBOWS
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1. Barangay Health Worker (BHW) Program Republic Act No. 7883 What is it? * A community-based health initiative. * Trains local volunteers to provide primary healthcare services and health education at the barangay level. Green Modern Professional Environmental Awareness Presentation.pdf Why is it needed? * Helps communities with limited healthcare access. * Connects families with health centers and healthcare providers. * Brings basic healthcare closer to residents. Green Modern Professional Environmental Awareness Presentation.pdf Who implements it? * Department of Health (DOH) * Local Government Units (LGUs) * Local Health Boards Green Modern Professional Environmental Awareness Presentation.pdf Who benefits? * Barangay Health Workers * Underserved communities * Families and community members Green Modern Professional Environmental Awareness Presentation.pdf Importance / benefits * Makes basic healthcare more accessible. * Provides health education. * Helps identify health problems early. * Improves connections between residents and healthcare providers. Green Modern Professional Environmental Awareness Presentation.pdf Roles of BHWs * Provide basic health services. * Give health information and education. * Monitor community health. * Assist in disease prevention. * Encourage residents to seek proper healthcare. Green Modern Professional Environmental Awareness Presentation.pdf Penalties/fines: Not specified in the presentation. ⸻ 2. Magna Carta of Women Republic Act No. 9710 What is it? * A comprehensive Philippine human-rights law. * Signed on August 14, 2009. * Seeks to eliminate discrimination against women by recognizing, protecting, fulfilling, and promoting women’s human rights and fundamental freedoms, especially for marginalized women. magna carta of women.pdf Why was it implemented? 1. Fulfill international commitments * Helps the Philippines meet obligations under CEDAW. * Makes protection of women’s rights a domestic legal responsibility. 2. Address gender inequality * Requires government agencies to integrate women’s needs into planning. * Requires at least 5% of annual budgets for Gender and Development (GAD) programs. 3. Protect marginalized women * Includes farmers, fisherfolk, informal workers, indigenous groups, etc. * Provides rights involving land ownership, agricultural resources, social protection, and representation. magna carta of women.pdf Penalties * ₱10,000–₱50,000 fine for certain violations. * Serious violations: 1–6 months imprisonment. * Government officials who fail to enforce/protect women’s rights can face: * Formal warnings * Suspension without pay * Loss of employment magna carta of women.pdf Effects on community health * Barangays should have a VAW Desk providing crisis intervention, legal support, and psychosocial care. * Improves women’s access to public healthcare, maternal care, and family planning. * Provides up to 2 months paid special leave after gynecological surgeries. * Requires women’s representation in local development and health-planning bodies. magna carta of women.pdf Importance * Makes gender equality a legal responsibility of government. * Protects marginalized women and gives them access to resources, opportunities, and legal protection. Recommended improvements * Increase public awareness. * Strengthen enforcement and penalties. * Train barangay officials. * Hold officials accountable when complaints aren’t properly handled. ⸻ 3. Food Safety Act of 2013 Republic Act No. 10611 What is it? * Protects people from unsafe, contaminated, or harmful food. * Covers food safety from farm to fork, from production until food reaches consumers. * Strengthens food regulations and promotes proper food-handling practices. GROUP 6 FOOD SAFETY ACT.pdf Why is it needed? Without proper food-safety regulation, people can be exposed to foodborne illnesses and poisoning, including diseases such as: * Botulism * Hepatitis A * Listeriosis GROUP 6 FOOD SAFETY ACT.pdf Purpose * Protect consumer health. * Make sure local food supplies are properly checked. * Facilitate market access for safe food products. GROUP 6 FOOD SAFETY ACT.pdf Government agencies * FDA: processed/pre-packaged food. * DOH/LGUs: sanitation and food-service establishments. * DA: food safety in primary production such as crops, livestock, and fisheries. GROUP 6 FOOD SAFETY ACT.pdf Penalties First conviction * ₱50,000–₱100,000 fine * Suspension of authorization for 1 month Second conviction * ₱100,000–₱200,000 fine * Suspension for 3 months Third conviction * ₱200,000–₱300,000 fine * Suspension for 6 months If slight physical injury occurs * ₱200,000–₱300,000 fine * 6-month suspension * Offender also pays hospitalization and rehabilitation costs. GROUP 6 FOOD SAFETY ACT.pdf If serious/less serious physical injury occurs * ₱200,000–₱300,000 fine * 1-year suspension * Hospitalization and rehabilitation costs must also be paid. If death occurs * 6 months and 1 day to 6 years and 1 day imprisonment * ₱300,000–₱500,000 fine * Permanent revocation of authorization to operate the food business. GROUP 6 FOOD SAFETY ACT.pdf Recommended improvements * More frequent food inspections. * Better food-safety education in schools. * Food-safety campaigns and seminars. * Encourage people to follow food-safety practices. GROUP 6 FOOD SAFETY ACT.pdf ⸻ 4. Consumer Act of the Philippines Republic Act No. 7394 What is it? * Primary national law protecting consumer interests. * Protects product safety. * Establishes fair standards for businesses. * Signed April 13, 1992. Green Monochromatic Simple The Minimalist Presentation Template.pdf Main objectives * Protect consumers from hazardous/substandard products. * Ban deceptive, unfair, and unconscionable sales practices. * Provide clear product information. * Give consumers legal remedies when harmed. Green Monochromatic Simple The Minimalist Presentation Template.pdf Why was it needed? * Protect consumers from unsafe products. * Prevent unfair business practices. * Prevent misleading information. * Promote consumers’ health, safety, and economic interests. * Protect the right to information, safety, and fair treatment. Green Monochromatic Simple The Minimalist Presentation Template.pdf Positive effects * Protects against unsafe/substandard products. * Requires clear labeling, descriptions, ingredients, and expiration dates. * Bans false advertising and deceptive packaging. * Gives consumers ways to seek refunds, replacements, or damages. Green Monochromatic Simple The Minimalist Presentation Template.pdf Possible negative effects * Compliance costs can increase product prices. * Strict licensing/certification can be difficult for small businesses. * Fraudulent or exaggerated consumer claims can financially burden honest businesses. Green Monochromatic Simple The Minimalist Presentation Template.pdf Penalties * Selling banned/unsafe products: ₱1,000–₱10,000 fine, 2 months–1 year imprisonment, or both. * Certain medicine/medical-device violations: ₱5,000–₱10,000 fine, 1–5 years imprisonment, or both. * Warranty violations: ₱1,000–₱50,000 fine or 1–5 years imprisonment, or both. * Certain labeling/packaging violations: ₱500–₱20,000 fine, 3 months–2 years imprisonment, or both. Green Monochromatic Simple The Minimalist Presentation Template.pdf Government agencies * DTI: consumer products and unfair/deceptive trade practices. * DOH: food, drugs, cosmetics, medical devices. * DA: agricultural/fresh-food safety and labeling. Green Monochromatic Simple The Minimalist Presentation Template.pdf Improvements * Stronger protection against online scams and fake advertisements. * More consumer education about scams, false advertising, and safe products. Green Monochromatic Simple The Minimalist Presentation Template.pdf ⸻ 5. Safe Spaces Act Republic Act No. 11313, “Bawal Bastos Law” What is it? * Protects individuals from gender-based sexual harassment in: * Public spaces * Workplaces * Schools * Online environments. Health .pdf Passed * April 17, 2019 What is gender-based sexual harassment? Unwanted/unwelcome sexual acts, comments, gestures, or behavior directed at someone because of sex, gender, sexual orientation, gender identity, or gender expression. Health .pdf Examples * Catcalling/wolf-whistling * Unwanted sexual remarks * Sexist, homophobic, or transphobic slurs * Persistent unwanted invitations * Stalking * Unwanted sexual messages * Certain sharing of photos/videos without consent. Health .pdf Why is it important? * Promotes safety, respect, dignity, and equality. * Recognizes that harassment can happen in public spaces, schools, workplaces, and online. Community effects * Creates safer communities. * Raises awareness. * Encourages respect for boundaries. * Provides reporting mechanisms. * Requires schools/LGUs to take action. * Provides support and protection for victims. Health .pdf Penalties Catcalling/verbal harassment * 1st offense: ₱1,000 + community service + Gender Sensitivity Seminar * 2nd offense: 6–10 days arrest OR ₱3,000 fine * 3rd offense: 11–30 days arrest + ₱10,000 fine Stalking * ₱30,000 fine or arrest for first offense, with higher penalties for repeat offenses. Online sexual harassment * ₱100,000–₱500,000 fine and/or imprisonment. Health .pdf Improvements * More awareness campaigns. * Clear reporting procedures. * Easier access to complaint desks/hotlines. * Regular gender-sensitivity seminars. * More training for teachers, barangay officials, and enforcers. * Better complaint documentation/follow-up. Health .pdf ⸻ 6. Expanded Program on Immunization EPI What is it? * A public-health program designed to protect people, especially children, from vaccine-preventable diseases through recommended vaccines. Expanded Program on Immunization.pdf History * Global EPI launched by WHO in 1974. * Developed into the Essential Programme on Immunization, covering vaccination throughout life. Expanded Program on Immunization.pdf Philippines * Implemented through the DOH National Immunization Program (NIP) with LGUs and health facilities. Expanded Program on Immunization.pdf Why was it established? Many infectious diseases caused: * Illness * Disability * Death, especially among children. Vaccination provides immunity before exposure and helps prevent outbreaks. Expanded Program on Immunization.pdf Main objectives * Protect infants, children, pregnant women, and other priority groups. * Increase immunization coverage. * Give vaccines at recommended ages/intervals. * Prevent outbreaks. * Reduce illness, disability, and deaths. * Reach communities with limited healthcare access. Expanded Program on Immunization.pdf Diseases mentioned * Tuberculosis * Hepatitis B * Diphtheria * Pertussis * Tetanus * Polio * Measles * Mumps * Rubella * Hib disease * Pneumococcal disease * HPV-related diseases. Expanded Program on Immunization.pdf How it works * Vaccines train the immune system to recognize specific pathogens. * High vaccination coverage reduces disease transmission and can help protect people who cannot receive certain vaccines or don’t develop adequate immunity. Expanded Program on Immunization.pdf Challenges * Limited healthcare access. * Vaccine hesitancy/misinformation. * Missed or delayed appointments. * Supply/logistical problems. * Health-system barriers. * Emergencies/disruptions. Improvements * Improve access in remote areas. * Community/mobile vaccination. * Catch-up vaccination. * Better vaccine supply, transportation, and cold-chain management. * Train/support healthcare workers. * Better immunization records. * Accurate health education. * Counter misinformation. * Stronger disease surveillance and outbreak response. Penalties: Not specified because this is a health program rather than a presentation focused on criminal sanctions. ⸻ 7. Responsible Parenthood and Reproductive Health Act Republic Act No. 10354 What is it? * Establishes a national system for healthcare, education, and support concerning: * Pregnancy * Childbirth * Family planning * Sexual health. PE - Group 7.pdf What does it cover? * Maternal and newborn care. * Family-planning methods. * Health education. * Access to healthcare facilities/professionals. * Adolescent health guidance. PE - Group 7.pdf Why was it signed? * Address health and population concerns. * Improve access to healthcare and information. * Reduce preventable deaths related to pregnancy/childbirth. * Help families make informed decisions about having children. * Address poor and marginalized communities. * Establish government responsibilities for these services. PE - Group 7.pdf Penalties Under Section 24, the presentation lists: * ₱10,000–₱100,000 fine * 1–6 months imprisonment * Some public-official violations may result in suspension or removal from office. * Other violations have specific penalties. PE - Group 7.pdf Effects on community health * Better care before/after childbirth. * Better newborn and child healthcare. * Greater access to family planning. * Adolescent health guidance. * Additional support for people who struggle to access healthcare. PE - Group 7.pdf Why it matters * Pregnancy/childbirth can involve serious health risks. * Lack of healthcare access can worsen those risks. * Unplanned pregnancies can create additional challenges. * Misinformation can lead to poor decisions. * Poor and remote communities may have fewer healthcare options. PE - Group 7.pdf Improvements * Expand services in remote areas. * Strengthen monitoring. * Update educational materials. * Increase healthcare-worker training, especially in underserved areas. PE - Group 7.pdf ⸻ 8. National Health Insurance Program NHIP / RA 7875, expanded through RA 11223 What is it? * Government initiative intended to provide universal health-insurance coverage and financial protection against medical costs. * Enacted in 1995 under RA 7875. * Coverage was expanded through the Universal Health Care Act (RA 11223), including automatic enrollment of Filipino citizens at birth. Soft Pink Elegant Scrapbook Creative Portfolio Presentation.pdf Why was it implemented? * Make healthcare financially accessible. * Help people who cannot afford healthcare. * Provide government subsidies for indigent members. * Achieve universal health-insurance coverage. * Promote equality in healthcare access. * Share the financial burden of healthcare. Who is involved? * DOH: policy coordination/guidance and healthcare regulation. * PhilHealth: main implementer/administrator, including membership, contributions, benefits, claims, and provider accreditation. * LGUs: local implementation, enrollment support, subsidies, and access. * DSWD: helps identify indigent/vulnerable Filipinos who may qualify. Positive effects * Increased access to healthcare. * Reduces financial burden from medical emergencies. * Encourages preventive healthcare. * Particularly helps people with limited ability to pay. Problems/issues * Benefits may not cover all healthcare expenses. * Unequal healthcare access between regions. * Claims and administrative problems can cause delays or denials. Recommended improvements * Reduce out-of-pocket expenses. * Expand healthcare access, especially rural clinics. * Expand preventive care such as screenings, vaccinations, checkups, and health education. * Improve electronic claims processing. Penalties: Not specified in this presentation. ⸻ 9. Ecological Solid Waste Management Act Republic Act No. 9003 What is it? * Environmental law focused on proper solid-waste management. Why was it needed? * Non-biodegradable waste polluted waterways and marine ecosystems. * Clogged drainage contributed to localized flooding. * Rapid urbanization and single-use packaging created huge amounts of waste that local systems struggled to handle. Group 4 RA 9003.pdf When established? * Passed by Congress: December 20, 2000 * Approved: January 26, 2001 Group 4 RA 9003.pdf Who is involved? * Provinces/MMDA * Cities/municipalities * Barangays * NGOs * Manufacturers/recyclers * Private contractors * Households and businesses. Group 4 RA 9003.pdf Implementation * Multi-level governance. * Mandatory waste segregation at source. * Materials Recovery Facilities (MRFs). * Closure of open/unmanaged dumpsites. * Penalties for prohibited acts. Group 4 RA 9003.pdf Penalties Violation Penalty Littering/dumping ₱300–₱1,000 + 1–15 days community service Improper collection/transport or open burning ₱300–₱1,000 + 1–15 days jail Non-segregated collection, squatting in dumpsites, dumping in flood-prone areas, unauthorized recycling removal ₱1,000–₱3,000 + 15 days–6 months jail Mixing recyclables, operating open dumps, non-eco packaging/importing non-eco packaging ₱500,000 + 5–10% income Importing toxic waste/unauthorized disposal ₱10,000–₱200,000 + 30 days–3 years jail Illegal waste facility/building near dumpsites/landfill on aquifer or watershed ₱100,000–₱1 million + 1–6 years jail EPR noncompliance ₱5 million–₱20 million + possible permit suspension These sanctions are listed in the presentation. Group 4 RA 9003.pdf Positive effects * Cleaner and safer surroundings. * Better air quality. * Green jobs/income. * Stronger barangay leadership. * Better waste-management habits. Group 4 RA 9003.pdf Negative effects * Higher costs for households/LGUs. * Inconvenience from segregation. * Improper disposal if facilities aren’t adequate. * Strain on local governments. * Dumpsite closures can create short-term problems. Group 4 RA 9003.pdf Recommendations * Enforce Extended Producer Responsibility. * Make manufacturers/distributors responsible for post-consumer plastic packaging. * Fund and require functioning barangay MRFs for composting and recycling. Group 4 RA 9003.pdf ⸻ 10. Philippine Clean Air Act Republic Act No. 8749 What is it? * Law intended to protect human health and the environment by controlling/reducing air pollution from: * Vehicles * Factories * Other pollution sources. Group 3.pdf Why is it needed? * Reduces air pollution. * Protects public health. * Sets rules for pollution from vehicles, factories, and other sources. * Gives people the right to breathe clean air. Group 3.pdf Sources of air pollution mentioned * Burning fossil fuels. * Automobiles. * Agricultural activities. * Factories and industries. * Mining activities. Effects * Air pollution can damage human health. * Industrial emissions degrade air quality. * Mining dust/chemicals can affect workers and nearby communities. How to improve air quality * Use renewable energy. * Limit fossil-fuel use. * Adopt sustainable habits. * Strengthen vehicle-emission regulations. * Control nitrogen oxides and fine particles. * Use technologies that reduce brake-related particles. The presentation says TAMIC® can reduce brake particles by 70–90%. Group 3.pdf Penalties The presentation divides violations into categories. Motor-vehicle violations * ₱10,000–₱100,000 per day of violation. * 6 months–1 year imprisonment. * Business operations may be suspended or closed. Gross violations * ₱100,000–₱1,000,000 per day. * 6–10 years imprisonment. * Business may be permanently closed. * Government officials may be dismissed or disqualified from office. The presentation describes gross violations as including things such as multiple violations within a year, ignoring DENR closure orders, or causing serious environmental damage. ⸻ Law / Program Key number BHW Program RA 7883 Magna Carta of Women RA 9710 Magna Carta GAD budget 5% Magna Carta fines ₱10k–₱50k Magna Carta imprisonment 1–6 months Food Safety Act RA 10611 Food Safety 1st conviction ₱50k–₱100k + 1 month suspension Food Safety 2nd ₱100k–₱200k + 3 months suspension Food Safety 3rd ₱200k–₱300k + 6 months suspension Food Safety death 6 months + 1 day to 6 years + 1 day Food Safety death fine ₱300k–₱500k Consumer Act RA 7394 Consumer unsafe products ₱1k–₱10k / 2 months–1 year Consumer medicine/device violations ₱5k–₱10k / 1–5 years Safe Spaces Act RA 11313 Safe Spaces 1st catcalling ₱1k + community service + seminar Safe Spaces 2nd 6–10 days or ₱3k Safe Spaces 3rd 11–30 days + ₱10k Safe Spaces online harassment ₱100k–₱500k +/or imprisonment EPI Global launch 1974 RH Law RA 10354 RH Law penalties ₱10k–₱100k / 1–6 months NHIP RA 7875 UHC expansion RA 11223 Ecological Solid Waste Act RA 9003 RA 9003 littering ₱300–₱1k + 1–15 days community service RA 9003 toxic waste ₱10k–₱200k + 30 days–3 years RA 9003 major violations ₱100k–₱1M + 1–6 years RA 9003 EPR noncompliance ₱5M–₱20M Clean Air Act RA 8749 Clean Air motor violations ₱10k–₱100k/day + 6 months–1 year Clean Air gross violations ₱100k–₱1M/day + 6–10 years
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Chapter 10: Stress, Health, and Coping Stress vs. Stressor * Stressor: Anything that causes stress (an event, situation, or demand). * Example: Exams, losing a job, relationship problems. * Stress: The body’s response to a stressor. * Example: Feeling anxious, increased heart rate. Types of Stressors 1. Catastrophe * Large, unpredictable events affecting many people. * Example: Natural disasters, wars. 2. Significant Life Changes * Major events that require adjustment. * Example: Divorce, moving, starting college. 3. Daily Stressors * Small everyday problems. * Example: Traffic, homework, arguments. Sympathetic Nervous System & Fight-or-Flight * Activates during stressful situations. * Prepares the body to react. * Causes: * Increased heart rate * Faster breathing * More energy released General Adaptation Syndrome (GAS) A three-stage response to stress: 1. Alarm: Body reacts to stress. 2. Resistance: Body tries to adapt and continue functioning. 3. Exhaustion: Long-term stress drains resources. Type A vs. Type B Personality Type A: * Competitive * Impatient * Time-urgent * More stress-prone Type B: * Relaxed * Patient * Less stressed Immune System & Stress * Long-term stress weakens the immune system. * Makes the body more vulnerable to illness. Locus of Control Internal locus of control: * Belief that you control your outcomes. External locus of control: * Belief that outside forces control outcomes (luck, fate). Managing Stress * Aerobic exercise * Meditation * Relaxation techniques * Spending time with pets * Social support * Healthy sleep habits ⸻ Chapter 11: Social Psychology Fundamental Attribution Error * Tendency to explain others’ behavior by personality instead of situations. * Example: “He’s lazy” instead of considering he may be exhausted. Attitudes * Feelings and beliefs that influence behavior. * Made of: * Thoughts * Feelings * Actions Cognitive Dissonance * Mental discomfort from having conflicting beliefs or behaviors. * Example: Knowing smoking is unhealthy but continuing to smoke. Social Contagion * Spread of behaviors, emotions, or ideas through groups. * Example: Panic spreading through a crowd. Classic Studies Asch’s Line Study * Showed people may conform to a group even when the group is wrong. Milgram’s Obedience Study * Showed people may obey authority figures even when uncomfortable. Social Facilitation vs. Social Loafing Social Facilitation: * Performance improves when others are watching. Social Loafing: * People put in less effort when working in groups. Deindividuation * Losing self-awareness and responsibility in a group. * Example: Crowds acting differently than individuals. Ingoups vs. Outgroups Ingroup: * Group you belong to. Outgroup: * Group you see as different. Can lead to: * Bias * Stereotypes * Prejudice Passionate vs. Companionate Love Passionate Love: * Intense attraction and excitement. Companionate Love: * Deep affection, trust, and commitment. Altruism & Bystander Effect Altruism: * Helping others without expecting a reward. Bystander Effect: * People are less likely to help when others are present. ⸻ Chapter 12: Personality Personality * Patterns of thoughts, feelings, and behaviors that make someone unique. Psychoanalytic Theory (Freud) Id * Wants immediate pleasure. * “I want it now.” Ego * Reality-based decision maker. * Balances id and superego. Superego * Morals and rules. Defense Mechanisms Ways the mind protects itself from anxiety. Examples: * Denial: Refusing to accept reality. * Projection: Blaming feelings on others. * Rationalization: Creating excuses. Humanistic Theory * Focuses on personal growth and reaching full potential. * Carl Rogers developed Person-Centered Therapy. Trait Theory (Big Five) Five major personality traits: OCEAN * Openness * Conscientiousness * Extraversion * Agreeableness * Neuroticism Spotlight Effect vs. Narcissism Spotlight Effect: * Believing others notice you more than they actually do. Narcissism: * Excessive self-focus and feeling superior. Kruger-Dunning Effect * People with low ability may overestimate their skills. Individualistic vs. Collectivistic Cultures Individualistic: * Focus on independence and personal goals. Collectivistic: * Focus on family, groups, and cooperation. ⸻ Chapter 13: Psychological Disorders Psychological Disorder * A pattern of thoughts, feelings, or behaviors that causes distress or problems functioning. Anxiety Disorders * Excessive fear or worry. Examples: * Generalized anxiety disorder * Panic disorder * Phobias OCD * Obsessions (unwanted thoughts) * Compulsions (repetitive behaviors) PTSD * Stress disorder after experiencing or witnessing trauma. Substance Use Disorder * Difficulty controlling substance use despite negative effects. Major Depressive Disorder Symptoms include: * Persistent sadness * Loss of interest * Changes in sleep or energy Bipolar Disorder * Episodes of depression and mania. * Mania involves unusually high energy, mood, or activity. Suicidal Ideation * Thoughts about suicide. (Important: any concerns about safety should be taken seriously and support should be reached out to.) Schizophrenia * Disorder involving: * Hallucinations * Delusions * Disorganized thinking Personality Disorders Antisocial PD * Disregard for others’ rights and social rules. Narcissistic PD * Extreme need for admiration and lack of empathy. Borderline PD * Difficulty with emotions, relationships, and sense of self. ⸻ Chapter 14: Treatment Psychotherapy * Treatment using psychological methods to improve mental health. Types of Psychotherapy Psychoanalysis/Psychodynamic * Focuses on unconscious conflicts and past experiences. Client-Centered/Humanistic * Focuses on acceptance, growth, and self-understanding. Behavioral Therapy * Changes behaviors through learning principles. Cognitive Therapy * Changes unhealthy thought patterns. Cognitive Behavioral Therapy (CBT) * Combines changing thoughts and behaviors. Family Therapy * Works with family relationships. Group Therapy * Therapy with multiple people. Evidence-Based Practice * Treatments supported by scientific research. Therapeutic Lifestyle Change Improving mental health through: * Exercise * Sleep * Nutrition * Social connection Biomedical Treatments Medication * Treats symptoms through biological processes. ECT (Electroconvulsive Therapy) * Uses controlled electrical stimulation to treat severe depression. Psychosurgery * Surgery involving the brain (rare). TMS (Transcranial Magnetic Stimulation) * Uses magnetic stimulation to affect brain activity. ⸻ Quick Test Tips: * Stress = response, Stressor = cause * Asch = conformity * Milgram = obedience * Big Five = OCEAN * Id = pleasure, Ego = reality, Superego = morals * CBT = thoughts + behaviors * Bystander effect = less helping in groups
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