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Reactions in Aqueous Solutions “A” students work (without solutions manual) ~ 10 problems/night. Alanah Fitch Flanner Hall 402 508-3119 [email protected] Water – the stuff of life and of the earth. Reactions – carried out in water, either as a bucket or glass of water or as adsorbed water onto surfaces. Types of common reactions precipitation acid-base oxidation-reduction reactions Office Hours W – F 2-3 pm All of above reactions involve IONS in solution and are affected by 1. Charge of ions 2. Size of ions 3. Number of ions/volume particles mass → particles → volume g → moles → molarity molarity ( M ) ≡ [ A] = moles of solute liters of solution moles A liters of solution Example: Solve either stepwise or chainwise. Stepwise If a bottle is labeled as concentrated hydrochloric acid (12.0 M) how many Moles are there in 50.0 mL? Concentrated [HCl] = 12.0M Moles in 50.0 mL [ HCl] = [ A] = moles A liters of solution 12.0molesHCl L ⎡ 12.0molesHCl ⎤ x= ⎢ ⎥⎦ 0.0500 L L ⎣ L ⎤ = 0.0500 L ⎣ 10 mL ⎥⎦ x = 0.600molesHCl ( 50mL) ⎡⎢ 3 12.0molesHCl xmolesHCl = L 0.0500 L Sig Figs Concentrated – relatively large (>?>6M) Dilute – relatively small (<?<0.1 M) 1 Example: Chainwise If a bottle is labeled as concentrated hydrochloric acid (12.0 M) how many Moles are there in 50.0 mL? [HCl] = 12.0M= known Moles in 50.0 mL= unknown 1L 12.0molesHCl ( 50.0mL) ⎡⎢ 3 ⎤⎥ = x ⎣ 10 mL ⎦ Suppose you need to react 0.25 mol of HCl with a second substance. What volume of 12.0 M HCl would you use? Need 0.25 mol HCl Stepwise solution ⎛ 12.0molesHCl ⎞ 0.25molHCl ⎜ ⎟ = ⎝ ⎠ 1L xL Chainwise solution xL = 0.25molHCl 3 3 1L ⎡ 1LL⎤ ⎤ ⎡⎤ 10 mL ⎤ ⎡⎤⎡⎡ 10 1mL .8333mL⎥ = 20 ⎛ 12.0molesHCl ⎞ 0.25molHCl0⎢0.025 molHCl .25 25 molHCl .12 molHCl ⎢ ⎥ ⎢ ⎥ ⎢ ⎥ ⎢ ⎥ L ⎦ ⎦ ⎣⎦ L ⎦ ⎣ moleHCl⎣⎦12 ⎜ ⎟ moleHCl ⎣⎣12moleHCl ⎝ ⎠ 1L xL = 0.25 L 12.0 L x = 0.600molesHCl Second substance Vol 12.0 M HCl unknown 20.8333mL = 21mL xL = 2.083x10−2 L ⎡ 10 3 mL ⎤ x mL = 2.083x10 − 2 L ⎢ ⎥ ⎣ L ⎦ Sig figs x mL = 20.83mL = 21mL Example. If you have 3.0 M PbCl2 what concentration of Cl- ions do you have? Most ionic compounds dissolve completely in water to the individual ions. NaCl( s) → NaCl( aq ) ⎯completely ⎯⎯⎯ ⎯→ Na(+aq ) + Cl(−aq ) NaCl( s) ⎯completely ⎯⎯⎯ ⎯→ Na(+aq ) + Cl(−aq ) + − PbCl2( s) → PbCl2( aq ) ⎯completely ⎯⎯⎯ ⎯→ Pb(2aq ) + 2Cl( aq ) + − PbCl2( s) ⎯completely ⎯⎯⎯ ⎯→ Pb(2aq ) + 2Cl( aq ) OJO!!!! – VERY IMPORTANT – Must conserve mass - Equation must balance + − PbCl2( s) ⎯completely ⎯⎯⎯ ⎯→ Pb(2aq ) + 2Cl( aq ) Treat as conversion factors − − ⎡ 3.0molesPbCl2 ⎤ ⎡ 2molesCl ⎤ ⎡ 6.0molesCl ⎤ ⎥ ⎢ ⎥ ⎢ 1molePbCl ⎥ = ⎢ 1L 1L ⎣ ⎦⎣ ⎣ ⎦ 2 ⎦ [Cl ] = 2[ PbCl ] − 2 The concentration of Cl- ion is double that of PbCl2 [ Cl ] = 2( 3.0) = 6.0 M − 2 Another example: Write the chemical equation for the solution of ammonium phosphate NH 4 + PO43− ( NH 4 ) 3 PO4 ( s ) We memorized these ions Molecular charge nuetrality requires These are the most common charges of Transition metal ions and aluminum completely ((NH ⎯ NH44))33PO PO ⎯⎯⎯⎯ ⎯⎯⎯⎯ ⎯→ → 3 NH4+( aq ) + PO43(−aq ) 4 (4s()s )⎯ completely 1: stoichiometry 3: 1 + + ⎡ molesPO4 ( s ) ⎤ ⎡ 3molesNH 4 ( aq ) ⎤ ⎡ molesNH 4 ( aq ) ⎤ = ⎢ ⎥ ⎢ ⎥ ⎢ ⎥ 1molePO L L ⎥⎦ ⎣ ⎦ ⎢⎣ 4( s) ⎥ ⎦ ⎣⎢ 3+ 3+ 2+, 4+ 3+ 2+ 2+ 2+ 2+ 2+ 2+ [ PO ]3 = [ NH ] 3− 4 1+ 2+ + 4 2+ What is the concentration of ammonium in solution compared to phosphate? Example Give concentration in molarity of each ion in 0.080 M zinc phosphate Zn3 ( PO4 ) 2 ( s ) → 3Zn(2aq+ ) + 2 PO43(−aq ) Stoichiometry 1: 3: Water – the stuff of life and of the earth. Reactions – carried out in water, either as a bucket or glass of water or as adsorbed water onto surfaces. 21 Types of common reactions ⎡ 0.080molesZn3 ( PO4 ) ⎤ ⎡ 3molesZn 2 + ⎤ 2 ⎢ ⎥⎢ ⎥ = 0.24molesZn 2 + L ⎢⎣ ⎥⎦ ⎢⎣ 1moleZn3 ( PO4 ) 2 ⎥⎦ ⎡ 0.080molesZn3 ( PO4 ) ⎤ ⎡ 2molesPO 2 − ⎤ 016 . molesPO42 − 2 4 ⎢ ⎥⎢ ⎥= . MPO43− = 016 L L ⎢⎣ ⎥⎦ ⎢⎣ 1moleZn3 ( PO4 ) 2 ⎥⎦ precipitation acid-base oxidation-reduction reactions Which Rules Apply? 3 General Chemistry Low Charge Density Intermediate Charge Density High Charge Density Who precipitates and who stays soluble? Depends upon who reacts with whom? FITCH Rules G1: Suzuki is Success G2. Slow me down G3. Scientific Knowledge is Referential G4. Watch out for Red Herrings G5. Chemists are Lazy C1. It’s all about charge C2. Everybody wants to “be like Mike” ⎛ qq ⎞ C3. Size Matters ⎟ E = k⎜ ⎝r +r ⎠ C4. Still Waters Run Deep C5. Alpha Dogs eat first 1 2 No NO3Group 1 cations (1+) Clean Cl- SO42- Oh Card me OH- CO32- PleeeeaSe!! S2- PO43- Weak Electrostatic Interaction = Soluble BaSO4 Mg(OH)2 Group 2 cations (2+) Transition metal cations (usually 2+) Socks AgCl Strong Electrostatic Interaction results in precipitation el 1 2 Example What happens when a solution of CuSO4 is mixed with a solution of NaNO3? What happens when a solution of Na2CO3 is mixed with a solution of CaCl2? First assume everbody goes into solution or already in solution Identify who is charge dense and who is not charge dense High/high always precipitates Low/low never precipitates Low/High generally does not precipitate No Clean Socks 2+ 2− + − aq 4 aq aq 3aq Group 1 Transition No Clean Socks Metal ion CuSO4 ( aq ) + NaNO3( aq ) → Cu + SO + Na + NO Extremes 1. Low -Low charge density ion interactions - weak electrostatic energy Stay soluble 2. High -High charge density ion interactions - strong electrostatic energy Precipitate 3. High- Intermediate charge density ion interactions – generally strong electrostatic energy – precipitate In Between 1. Low – High charge density ion interactions – generally weak electrostatic energy: Soluble with exceptions 2. Low – Intermediate charge density ion interactions – generally weak electrostatic energy: Soluble with exceptions 3. Intermediate – Intermediate – charge density ion interactions – generally weak electrostatic energy: soluble with exceptions Example. What happens when a solution of CuSO4 is mixed with a solution of NaNO3? What happens when a solution of Na2CO3 is mixed with a solution of CaCl2? Rx Oh Card me PleaSe + 2+ Na 2 CO3( aq ) + CaCl2 ( aq ) → 2 Na aq + CO32aq− + Ca aq + 2Claq− Group 1 Group 2 Group 17 + 2+ + 2 Na aq + 2Claq− + CO 2 − 3( aq ) + Ca aq → CaCO32s− + 2 Na aq + 2Claq− no reaction 4 Chemistry General FITCH Rules G1: Suzuki is Success G2. Slow me down G3. Scientific Knowledge is Referential G4. Watch out for Red Herrings G5. Chemists are Lazy C1. It’s all about charge C2. Everybody wants to “be like Mike” ⎛ qq ⎞ C3. Size Matters ⎟ E = k⎜ ⎝r +r ⎠ C4. Still Waters Run Deep C5. Alpha Dogs eat first Example. What happens when a solution of CuSO4 is mixed with a solution of NaNO3? What happens when a solution of Na2CO3 is mixed with a solution of CaCl2? Oh Card me PleaSe + aq 2+ Na 2 CO3( aq ) + CaCl2 ( aq ) → 2 Na + CO32aq− + Ca aq + 2Claq− Group 1 1 2 Do not write redundant (on both sides) ions Write NET ionic equation 2 2+ CO 2 − 3( aq ) + Ca aq → CaCO32s− Stoichiometry is important in these reactions Stoichiometry is important in these reactions Example : Consider the net ionic equation for the reaction that occurs when solutions of Cu(NO3)2 and NaOH are mixed. What volume of 0.106 M Cu(NO3)2 solution is required to form 6.52 g of solid Cu(OH)2? 1. Check for charge dense ions that can precipitate 2. Write a net ionic reaction which excludes spectators (low charge dense ions) 3. Count total moles of all precipitating reactants Cu(2+aq ) OH(−aq ) NO3(− aq ) Na Charge Dense Transition metal Cu(2+aq ) + OH (−aq ) + → CuOH x ( s) Oh, Card me Please – charge dense 2+ ( aq ) No Clean Socks – not charge dense + ( aq ) Group – not charge dense Cu + 2OH(−aq ) + → Cu( OH ) 2( s) Group 17 + 2+ + 2 Na aq + 2Claq− + CO 2 − 3( aq ) + Ca aq → CaCO32s− + 2 Na aq + 2Claq− el 1 Group 2 Example : Consider the net ionic equation for the reaction that occurs when solutions of Cu(NO3)2 and NaOH are mixed. What volume of 0.106 M Cu(NO3)2 solution is required to form 6.52 g of solid Cu(OH)2? − 2+ Cu( aq ) + 2OH( aq ) + → Cu( OH ) 2( s) 1: 2: 1 ⎡ 1moleCu(OH ) 2 ⎤ −2 ⎥ = 6.6823x10 moleCu(OH ) 2 2⎦ ⎣ [6.52 gCu(OH ) ]⎢ 97.57 gCu(OH ) 2 ⎡ moleCu ⎤ ⎡ moleCu( NO3 ) 2 ⎤ = 6.6823x10 − 2 moleCu( NO3 ) 2 6.6823x10 − 2 moleCu(OH ) 2 ⎢ ⎥⎢ moleCu ⎥⎦ ⎣ moleCu(OH ) 2 ⎦ ⎣ ⎡ 1LCu( NO3 ) 2 ⎤ −1 6.6823x10 − 2 moleCu( NO3 ) 2 ⎢ ⎥ = 6.304133849 x10 L 0106 . moleCu ( NO ) ⎣ 3 2⎦ ? = 0.630L 5 Stoichiometry is important in these reactions Stoichiometry is important in these reactions Example : Consider the net ionic equation for the reaction that occurs when solutions of Cu(NO3)2 and NaOH are mixed. What volume of 0.106 M Cu(NO3)2 solution is required to form 6.52 g of solid Cu(OH)2? Cu 2+ + 2OH − + → Cu( OH ) ( aq ) 2( s) ( aq ) Chainwise solution 52 gCu(OH ) ]⎡ 1moleCu(OH ) [[66..52 gCu(OH ) ]⎢ 97.57 gCu(OH ) 2 2 ⎤ ⎡ moleCu ⎤ ⎡ moleCu( NO3 ) 2 ⎤ ⎡ 1LCu( NO3 ) 2 ⎤ ⎢ ⎥=? ⎥⎢ ⎥⎢ moleCu ⎥⎦ ⎣ 0106 . moleCu( NO3 ) 2 ⎦ 2 ⎦ ⎣ moleCu( OH ) 2 ⎦ ⎣ 2 ⎣ ? = 6.304133849 x101 L ? = 0.630L Example: When aqueous solutions of sodium hydroxide and iron(III) nitrate are mixed, a red gelatinous precipitate forms. Calculate the mass of precipitate formed when 50.00 mL of 0.200 M NaOH and 30.00 mL of 0.125 M Fe(NO3)3 are mixed 1. Check for charge dense ions that can precipitate 2. Write a net ionic reaction which excludes spectators (low charge dense ions) 3. Count total moles of all precipitating reactants Fe(III) Fe(3+aq ) + OH(−aq ) + → Fe(OH ) x ( s) Fe 3+ + 3OH − + → Fe(OH ) 3( s ) ( aq ) ( aq ) OHCharge balance both sides of equation ⎡ 1L ⎤ ⎡ 0.200moleNaOH ⎤ 3 ⎥⎦ = 0.0100moleNaOH LNaOH ⎣ 10 mL ⎥⎦ ⎢⎣ [50mLNaOH ] ⎢ ⎡ 0125 . moleFe( NO3 ) 3 ⎤ ⎥ = 0.00375moleFe( NO3 ) 3 LFe( NO3 ) 3 ⎣ ⎦ [30.00mLFe( NO ) ]⎡⎢⎣ 101LmL ⎤⎥⎦ ⎢ 3 3 3 Stoichiometry is important in these reactions Water – the stuff of life and of the earth. Example: When aqueous solutions of sodium hydroxide and iron(III) nitrate are mixed, a red gelatinous precipitate forms. Calculate the mass of precipitate formed when 50.00 mL of 0.200 M NaOH and 30.00 mL of 0.125 M Fe(NO3)3 are mixed Moles present Fe 3+ OH- 0.00375 0.0100 1: Fe 3: 3+ ( aq ) + 3OH 1 − ( aq ) 0.00375 0.0100/3 = 0.00333 Smallest # is answer 1moleFe(OH ) 3 ⎤ ⎡ 10687 . gFe(OH ) 3 ⎤ 3+ ⎥ ⎢ 1moleFe(OH ) ⎥ = 0.356 gFe(OH ) 3 1 moleFe ⎣ ⎦⎣ 3 ⎦ [ 0.00333moleFe ]⎡⎢ 3+ could make moles product Reactions – carried out in water, either as a bucket or glass of water or as adsorbed water onto surfaces. Types of common reactions precipitation acid-base oxidation-reduction reactions Predicting who gets the proton (acid-base) depends on most charge dense of competing reactions + → Fe(OH ) 3( s) 6 Acid-Base Reactions Acid is a sour taste Foliate papillae are situated on the edge of the tongue slightly anterior of the circumvallate line. They are predominantly sensitive to sour tastes. Innervated by the glossopharyngeal (lXth cranial) nerve. On average 5.4 foliate papillae per side of the tongue, 117 taste buds per foliate papillae, total = 1280 foliate taste buds per tongue. Fatty acids and oils fill your skin. Carboxylate group – low charge density Bases dissolve Can be “bumped” by charge Dense OH- These compounds making soaps (feel slippery) + 3NaOH In 1849 a Harvard chemistry professor, John Webster argued with a colleague, Dr. Parkman, about money he owed the colleague for some dinosaur bones. He killed his fellow Professor and attempted to hide the crime by dissolving the body in a vat Of “lime” (Ca(OH)2) and then burning the remaining bones. (Or KOH) saponification + 3 CH3(CH2)14CO2Na glycerol A crude soap 7 Low Charge Density Intermediate Charge Density High Charge Density Who gives up and who holds onto a proton? Chemical Definition of Acid/Base No Svante Arrhenius H+ Socks SO42- Low Charge Density Anions Give up protons X- is an anion who is partnered with the cation, H+ Oh Card me OH- CO32- H2O High Charge Density Anions hold onto protons PleeeeaSe!! PO43- S2- WEAK acids STRONG acids HX aq → Haq+ + X aq− Acid: HX Strong acid Cl- NO3- An acid is a species that produces proton ions in solution Solution Clean Weak to Intermediate HX aq → Haq+ + X aq− Weak acid Completely falls apart → HX aq ← Haq+ + X aq− X- tries to hold onto some protons Double arrow In a STRONG acid the anion can not provide enough electrostatic attraction to hold onto the H+ (proton) In a WEAK acid the anion is very charge dense and holds onto the H+ Another very common type of Weak Acid - ….COOH Some Weak Acids with COO- functional group (Carboxylate) Condensed Structural Formula gives a clue as to the Important Functional Group Blue represents negative charge causes potential field HCOOH What do you see? HCOOH Is the negative charge fully localized? O O Formic Acid (Ants) O Acetic Acid Vinegar HOAc (OAc = acetate) OH H3C Butanoic Acid O O H C H Dissociate temporarily H H Proton actually resides Somewhere between Two highly negatively Charged oxygen OH H3C OH HCOOH CH3COOH Will Be Used Over and Over In Example Problems CH3CH2CH2COOH Different modeler Gave opposite color scheme (Red = large neg charge) http://academic.reed.edu/chemistry/alan/ED/JCE/figlist.html 8 Low Charge Density Intermediate Charge Density High Charge Density Who gives up and who holds onto a hydroxide? Chemical Definition of Acid/Base No Svante Arrhenius MOH → OH + M Solution Strong acid H+ + aq Weak acid Strong base Socks SO42- Oh Card me OH- CO32- PleeeeaSe!! PO43- S2- WEAK acids STRONG acids Group 1 cations (1+) Strong Bases Base: Acid: HX Cl- NO3- An acid is a species that produces proton ions in solution A base is a species that produces hydroxide ions in solution − aq Clean Group 2 cations (2+) Weak base Weak bases are produced by an alternative manner Where M+ is some cation http://core.ecu.edu/phys/flurchickk/AtomicMolecularSystems/molecularStructures/molecularStructures.html net neutral Molecule ammonia, NH3 Is the charge evenly distributed? Is there a region of high charge Density? In this model blue is negative charge causing a potential field and red is Positive charge opposite potential field R + H2 O → RHaq+ + OH aq− R + H2 O → RHaq+ + OH aq− Write reaction to show the unbonded electrons on R (where R is N in ammonia) H 2 O+ : R → OHaq− + RHaq+ Write the reaction to show that electrons on R are attracted to proton on water HO ⋅ ⋅ H + : R → OH aq− + RH aq+ NH 3 + H2 O →← NH 4+ + OH − Nitrogen typically contains a set of unbonded electrons which give Large charge density near the N atom Compounds in which H on NH3 has been replaced by –C groups react Similarly NH3 CH3NH2 R C2H5NH2 (C2H5)2NH C6H5NH2 9 Equations for ACID/BASE Reactions NH3 NH3 + H 2 O →← NH 4+ + OH − In order to KNOW How MUCH acid or base is present we often react acids and bases together CH3NH2 CH 3 NH 2 + H2 O →← CH 3 NH 3+ + OH − (CH ) NH + H O (CH ) 3 2 → ← 3 2 NH 2+ + OH − Three types of reactions: Three types of reactions: Strong Acid + Strong Base Strong Acid + Weak Base Weak Acid + Strong Base SA/SB SA/WB WA/SB Chemists Are Lazy Notation (CH3)2NH Weak Acid Strong Base Reaction Strong Acid Strong Base Reaction WA/SB SA/SB SA SB HNO3( aq ) → H + ( aq ) − 3( aq ) + NO NaOH( aq ) → Na (+aq ) + OHaq− ) H(+aq ) + OH (−aq ) → H2 O → HX aq ← Haq+ + X aq− WA Do not react (Low Charge Density) Spectators Reactants are H+ and OH- Net ionic equation SA/SB Remember: double arrow means X- is charge dense and tries to hold H+ SB NaOH( aq ) → Na (+aq ) + OHaq− ) Add These 2 rx Spectator H aq+ + OHaq− → H 2 O Why is there a single arrow? We are indicating that the protons and hydroxides we added as HNO3 and NaOH Are not going back to NO3- and Na+ . Proton and hydroxide must find each other and react HX aq + OHaq− → H 2 O + X aq− Net Ionic equation SB/WA HFaq + OH aq− → H2 O + Faq− example 10 Strong Acid Weak Base Reaction WA/SB Remember: double arrow means an incomplete reaction → Raq + H2 O ← OHaq− + RHaq+ WB SA HX → H aq+ + X aq− add Ous = least number of oxygen NaOH; Na+ is group 1 HNO3 is nitric acid so nitrous acid would be HNO2 Low charge density cation Na+ can not hold onto OH- NO3- Strong base Low charge density anion Higher charge density anion Probability: wants to hold onto H+ Probability: weak acid HX ( aq ) + OH − ( aq ) → X Net Ionic Eq Strong Acid Strong Base SA/SB H+, OH- H (+aq ) + OH(−aq ) → H2 O Weak Acid Strong Base WA/SB HX, OH- HX ( aq ) + OH (−aq ) → X (−aq ) + H2 O Strong Acid Weak Base SA/WB H +, R R( aq ) + H(+aq ) → HR(+aq ) example Example : Write a net ionic equation for each of the following reactions in dilute water solution Nitrous acid with sodium hydroxide vs Reacting Species Net Ionic equation SB/WA NH3aq + Haq+ → NH4+aq NO2- Reactants Spectator H aq+ + OHaq− → H 2 O Raq + Haq+ → RHaq+ Table Reaction is WA/SB − ( aq ) + H2 O HNO2 ( aq ) + OH(−aq ) → NO2−( aq ) + H2 O Example : Write a net ionic equation for each of the following reactions in dilute water solution Ethylamine (CH3CH2NH2) with perchloric acid HClO4 CH3CH2NH2 is an amine No Clean Socks Cl- and ClO4- N on amine has local negative charge perchlorate ion is 5 atom with single charge, electrons spread out over oxygen implies it is low charge dense, can’t hold N reacts with water to proton. steal a proton and leave Strong acid a hydroxide Reaction is SA/WB Weak Base R( aq ) + H (+aq ) → HR(+aq ) CH3CH 2 NH 2 + H(+aq ) → CH3 CH 2 NH 3+( aq ) 11 Example : Write a net ionic equation for each of the following reactions in dilute water solution Hydrobromic acid (HBr) with potassium hydroxide Br is group 17 K is group 1 Group 17 are singly charged Group 1 are singly charged Br is one charge/1 atom K is one charge/1 atom HBr = strong acid KOH= strong base Knowing HOW MUCH stuff is present How acidic is vinegar? Is tasting the way to go? Reaction is SA/SB H (+aq ) + OH(−aq ) → H2 O Types of problems: At Equivalence Point Solve for volume Solve for Molarity Solve for Mass Solve for moles [ A] = molarity nA VA [ A] = nA VA m A = n A MM A m A = n A MM A Moles of acid mass Stoichiometry n H ,eq pt = nOH ,eq pt Moles protons Volume Na+ - weak charge density = Strong base Acetic Acid CH3COOH = weak acid HX ( aq ) + OH(−aq ) → X (−aq ) + H 2 O [ ] aq Moles of Base moles ⎛ 1 ⎞ mB ⎜ ⎟ = nB ⎝ MM B ⎠ 0.8333mol = 0.833 M L + OH(−aq ) → CH 3COO(−aq ) + H 2 O 1: nB [ B] n H ,eq pt = nOH ,eq pt 25.0 mL 0.500 M NaOH Titrate Vinegar = Acetic Acid 15.0 mL Acetic Acid Molarity? H CH3 COO Moles OH VB = Example : In a titration it is found that 25.0 mL of 0.500 M NaOH is required to react with a 15.0 mL sample of vinegar. What is the molarity of acetic acid in the sample? 1; [[ ]] 1: 1 CH 3COO COOequivalencepo equivalencepoint mole⎞⎞ intmole moleNaOH ⎞⎛⎛ H CH ⎛ 1L ⎞ ⎛ 0.500moleNaOH ⎞ ⎟ HCH3 COOequivalencepo int mole 3 25mLNaOH mLNaOH )⎛⎛⎜ 11LL3 ⎞⎞⎟⎟⎛⎛⎜⎜00..500 500moleNaOH ⎞⎞⎟⎟⎛⎜⎜⎜H −3 (( (25 3 .152 ( 25mLNaOH LNaOH ⎟⎠⎠⎜⎜⎝ NaOHequivalencepo NaOHequivalencepoint mole ⎟ ⎟⎟⎟⎠ = 152 intmole 1033 mL mL⎟⎠⎠⎜⎝⎝ 11LNaOH 25 mLNaOH )) ⎜⎜⎝)⎝10 x10 −molH molHCH CH3COO . x10 3 COO 1LNaOH ⎠ ⎝ NaOHequivalencepo int mole ⎠ ⎠ = 10 mL ⎠ ⎝ 0.015 L 0.015 LH CH 3COO [ [ ] [[ ]] 12 Example : The principal ingredient of certain commercial antacids is calcium carbonate, CaCO3. A student titrates an antacid tablet weighting 0.542 g with hydrochloric acid; the reaction is Example : The principal ingredient of certain commercial antacids is calcium carbonate, CaCO3. A student titrates an antacid tablet weighting 0.542 g with hydrochloric acid; the reaction is CaCO3( s) + 2 H(+aq ) → Ca (2aq+ ) + CO2 ( g ) + H2 O CaCO3( s) + 2 H(+aq ) → Ca (2aq+ ) + CO2 ( g ) + H2 O If 38.5 mL of 0.200 M HCl is required for complete reaction, what is the percentage of CaCO3 in the antacid table? If 38.5 mL of 0.200 M HCl is required for complete reaction, what is the percentage of CaCO3 in the antacid table? ⎡ 0.3853gCaCO3( s) ⎤ ⎤ . stoichiometry ⎢ 0.542 gtablet ⎥ 100 = 71097% 100 ⎢ gtablet ⎥ ⎣ ⎦ ⎣ ⎦ 711% . Want: ⎡ gCaCO Before we start 1. Problem is slightly unusual because of gas production CO32aq− + H(+aq ) → HCO3−aq1 H2 O H+ OHaq− + CO2 g http://academic.reed.edu/chemistry/alan/ED/JCE/figlist.html Notice the “pinch point” Where there is little electron density = Weak bond What do you predict happens? CO32- Aqueous reactions with In presence of protons result in gas 3( s ) Need g CaCO3 + ⎡ 1L ⎤ ⎡ 0.200molesHCl ⎤ ⎡ 1moleH ⎤ ⎡ 1moleCaCO ⎤ ⎡ 100.09 gCaCO ⎤ ⎡ 1L ⎤ ⎡ 0.200molesHCl ⎤ 3 3 [ 38 38..55mLHCl mLHCl ] ⎢ 3 mL ⎥ ⎢ ⎥⎦ ⎢ moleHCl ⎥ ⎢⎣ 2moleH + ⎥⎦ ⎢ moleCaCO ⎥ = gCaCO3 ⎣ 10 1LHCl ⎦⎣ ⎣ ⎦ 3 ⎦ ⎣ FITCH Rules Chapter 4: Reactions in Aqueous Solutions General Water – the stuff of life and of the earth. Reactions – carried out in water, either as a bucket or glass of water or as adsorbed water onto surfaces. Why you must spend taxes to maintain not to build Chemistry Types of common reactions precipitation acid-base oxidation-reduction reactions Moles HCl equivalence pt Need Moles CaCO3 G1: Suzuki is Success G2. Slow me down G3. Scientific Knowledge is Referential G4. Watch out for Red Herrings G5. Chemists are Lazy C1. It’s all about charge C2. Everybody wants to “be like Mike” ⎛ qq ⎞ C3. Size Matters ⎟ E = k⎜ ⎝r +r ⎠ C4. Still Waters Run Deep C5. Alpha Dogs eat first 1 2 el 1 2 13 Net ionic reaction (excludes spectators) zinc reduces the protons = a reducing agent Zn( s) + 2 H(+aq ) → Zn(2aq+ ) + H2 ( g ) protons oxidize the zinc = oxidizing agent For convenience split Zn( s) → Zn(2aq+ ) + 2e 2 H (+aq ) + 2e → H2 ( g ) Oxidation (loss of electrons) increase in positive chargec Reduction (gain of electrons) (reduction in the positive charge on the ion) VERY IMP #1. - can’t really have 1/2 reaction because the electrons need to go somewhere!!!! OIL - Oxidation is Losing Electrons RIG Reduction is Gaining Electrons They are TOO Charge dense To exist in solution VERY IMP #2 - no net change in number of electrons (corollary of VERY IMP #1 - if we “lose” 2 need to “gain” 2 Writing the Net Ionic Reaction of an Oxidation-Reduction Reaction Track the oxidation numbers of the various species Writing the Net Ionic Reaction of an Oxidation-Reduction Reaction Track the oxidation numbers of the various species Oxidation Numbers Oxidation Numbers 1. Ox # of an element in an elementary substance is zero O2 Ox# = 0 Cl2 Ox# Cl =0; 2. Ox # of an element in a monatomic ion = charge of ion Cl- Na+ 3. Group 1 always +1 = always Ox # +1 Group 2 always +2 = always Ox# +2 1. F = -1 (always) Other halogens = -1 (usually) unless oxyanions ClO4- Ox# of Cl = +7 O= -2, with exceptions H = +1, with exceptions (when bonded to a nonmetal) 2. 3. Ox # of an element in an elementary substance is zero Cl2 Ox# Cl =0; O2 Ox# = 0 Ox # of an element in a monatomic ion = charge of ion ClNa+ Group 1 always +1 = always Ox # +1 Group 2 always +2 = always Ox# +2 F = -1 O= -2, with exceptions H = +1, with exceptions 4. Sum of Ox #=charge charge on molecule or ion 14 Writing the Net Ionic Reaction of an Oxidation-Reduction Reaction Oxidation numbers in Split into Reactions to be balanced PbO PbO2 Pb3O4 litharge, lead oxide platternite, lead dioxide minium, trilead tetraoxide Oxygen (with some exceptions) is -2 Pb3O4 PbO PbO2 ? + -2= 0 ? = +2 3(?) +4(-2) = 0 ? + 2(-2) = 0 3(?) + -8 = 0 ? = +4 This one is an oddity!!!! Need to know that lead only adopts +2 or +4 oxidation numbers Write oxidation half reaction Write reduction half reaction A. Balance atoms of element oxidized b. Balance Rx sides by adding e c. Balance charge by adding H+ or OHd. Balance hydrogen by adding H2O e. Balance oxygen A. Balance atoms of element reduced b. Balance Rx sides by adding e c. Balance charge by adding H+ or OHd. Balance hydrogen by adding H2O e. Balance oxygen 2(+2) + (+4) = -8 Writing the Net Ionic Reaction of an Oxidation-Reduction Reaction Combine and balance electrons Example: Balance the following redox equation in an acidic solution Fe(2aq+ ) + MnO4−( aq ) → Fe(3aq+ ) + Mn(2aq+ ) Reaction to be balanced Write oxidation half reaction Ox #balance 2+ 3+ Write reduction half reaction A. Balance atoms of element A. Balance atoms of element reduced oxidized b. Balance Ox number with e b. Balance Ox number with e c. Balance charge by adding H+ c. Balance charge by adding H+ or OHor OHProtons are added d. Balance hydrogen by adding d. Balance hydrogen by adding in an acidic solution H2O H2O e. Balance oxygenand hydroxyls are e. Balance oxygen added in a basic solution. Combine and balance electrons When in doubt add protons Fe 2+ ( aq ) → Fe +7 − 4 ( aq ) MnO 3+ ( aq ) +2 → Mn(2aq+ ) Mass balance Mass balance Fe 2+ ( aq ) 3+ ( aq ) → Fe ox# balance +e -1 = 4(-2) +? 8-1 = ? 7=? +2 MnO4−( aq ) + 5e → Mn(2aq+ ) 15 Example: Balance the following redox equation in an acidic solution Fe(2aq+ ) + MnO4−( aq ) → Fe(3aq+ ) + Mn(2aq+ ) 2+ 3+ +7 − 4 ( aq ) MnO Fe(2aq+ ) → Fe(3aq+ ) Example: Balance the following redox equation in an acidic solution Fe(2aq+ ) + MnO4−( aq ) → Fe(3aq+ ) + Mn(2aq+ ) +2 → Mn(2aq+ ) Fe(2aq+ ) → Fe(3aq+ ) + e Balance hydrogen by adding water Mass balanced Mass balanced Fe(2aq+ ) → Fe(3aq+ ) + e − Ox numbers 2 + 4 ( aq ) ( aq ) MnO + 5e → Mn MnO4−( aq ) + 5e + 8 H(+aq ) → Mn(2aq+ ) + 4 H2 O Check oxygen balance 4O +2 -1 + -5 = -6 Charge balance MnO4−( aq ) + 5e + 8 Haq + → Mn(2aq+ ) Example: Balance the following redox equation in an acidic solution Fe(2aq+ ) + MnO4−( aq ) → Fe(3aq+ ) + Mn(2aq+ ) Fe(2aq+ ) → Fe(3aq+ ) + e MnO4−( aq ) + 5e + 8 H(+aq ) → Mn(2aq+ ) + 4 H2 O Recombine while balancing electrons 5Fe(2aq+ ) → 5Fe(3aq+ ) + 5e MnO4−( aq ) + 5e + 8 H(+aq ) → Mn(2aq+ ) =+2 =4O Check total charge balance: (-1)+5(-1)+8(+1)=+2 Example: Balance the following redox equation in an acidic solution Fe(2aq+ ) + MnO4−( aq ) → Fe(3aq+ ) + Mn(2aq+ ) Fe(2aq+ ) → Fe(3aq+ ) + e MnO4−( aq ) + 5e + 8 H(+aq ) → Mn(2aq+ ) + 4 H2 O 5Fe(2aq+ ) → 5Fe(3aq+ ) + 5e MnO4−( aq ) + 5Fe(2aq+ ) + 8 H(+aq ) → 5Fe(3aq+ ) + Mn(2aq+ ) + 4 H2 O Final equation does not show any electrons because electrons do not exist in solution 16 MnO4−( aq ) + 5Fe(2aq+ ) + 8 H(+aq ) → 5Fe(3aq+ ) + Mn(2aq+ ) + 4 H2 O 0.250moleFe( NO3 ) 2 ⎡ ⎤ moleFe ⎡⎡ ⎡⎡ 1111LLLL ⎤⎤ ⎡⎡⎤⎤ 0⎡⎡ .00250 250moleFe moleFe NO)3 )) 2⎤⎤ ⎡⎤⎤ ⎡⎡ 11moleFe moleMnO4⎤ ⎤⎤ ⎡⎡ 11moleKMnO moleKMnO4 ⎤⎤ ⎡ LKMnO4 1moleFe ⎤ ⎡⎤⎤ ⎡⎡ 11moleMnO (( NO moleFe( NO 1L ⎤⎥ ⎢ ..250 mLFe NO [[27 ⎢ 1moleFe ⎥⎥ ⎢⎥ 1⎢moleMnO 27 ((( NO ( NO )))3 )]]2)⎡⎢⎣⎢]10 [27[...27505050.50.mLFe ⎥ ⎥⎢ 50mLFe mLFe ( NO ⎥⎢ moleFe(( NO NO )) ) ⎦ 5moleFe mL 27 mLFe NO ⎥⎦⎥ ⎢⎣⎥ 11⎢moleFe 3 mL⎥⎥⎦ ⎢⎣⎥ ⎢ ⎢⎣⎣]10 1111LLLL mL ⎣⎣⎢ 10 ⎦ ⎣⎦⎦ ⎣ 11moleFe moleFe(( NO NO ) ⎦ ⎣⎦ ⎣ 55moleFe 10mL mL⎦⎦ ⎣⎦⎦ ⎣⎣ moleFe 2+ ⎦ ⎦ ⎣ 11moleMnO moleMnO − ⎦ 0.684moleKMnO 10 3 2 333 3 2223 2 2 333 3 3 2 +2 + 2 +2 + 33 3 22 2 ⎣ 3 2 3 332 22 ⎦⎣ − −− 44 2 +2 + 4 − ⎦⎣ 44 ⎦⎣ 4 ⎤ −3 ⎥ = 2.01x10 LKMnO4 ⎦ = 2.01x10 −3 LKMnO4 Vol KMnO4? Moles MnO4- Moles Fe2+ General What volume of 0.684 M KMnO4 is required to react completely with 27.50 mL of 0.250 M Fe(NO3)2 Chemistry Having balanced the equation we can know predict or measure quantities that should react. FITCH Rules G1: Suzuki is Success G2. Slow me down G3. Scientific Knowledge is Referential G4. Watch out for Red Herrings G5. Chemists are Lazy C1. It’s all about charge C2. Everybody wants to “be like Mike” ⎛ qq ⎞ C3. Size Matters ⎟ E = k⎜ ⎝r +r ⎠ C4. Still Waters Run Deep C5. Alpha Dogs eat first 1 2 el 1 2 stoichiometry “A” students work (without solutions manual) ~ 10 problems/night. Alanah Fitch Flanner Hall 402 508-3119 [email protected] Office Hours W– F 2-3 pm 17