Acids. E5 Lewis Acids and Bases. Acids. Bronsted: Acids are proton donors. Session one. Problem Compounds containing cations other than H + are acids!

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1 E5 Lewis Acids and Bases Session one Pre-lab (p.141) due at start of lab. our 1: Discussion of E4 ours 2 & 3: Lab (Parts 1and 2A) Session two Lab: Parts 2B, 3 and 4 Acids Bronsted: Acids are proton donors. Problem Compounds containing cations other than + are acids! Acids Cations other than + generate hydronium ions in aqueous solution! Example: Al 3+ (aq) = p 3! Lewis Definition of Acids and Bases Define acid/base without using the word proton: Cl- + O Cl - + O Acid Base Base Acid A BASE DONATES unbonded ELECTRON PAIR/S. An ACID ACCEPTS ELECTRON PAIR/S. Deodorants and acid loving plant foods contain aluminum salts 1

2 Lewis Acids Electron deficient species ; potential electron pair acceptors. Examples: + Cu 2+ Al 3+ Lewis Bases Electron rich species; electron pair donors. I m deficient! Ammonia hydroxide ion water (ammine) (hydroxo) (aquo) Acid Lewis Acid-Base Reactions Lewis Acids: Metal Ions Example + + O + O Metal ions react with/bond to water molecules to form aquo complex ions in aqueous solution. Example: [Na( 2 O) 6 ] + Acid + Base Complex ion The acid reacts with the base by bonding to one or more available electron pairs on the base. The acid-base bond is a coordinate covalent bond. The product is a complex or complex ion 2

3 Aquo Complex Ions Aquo Complex Ions When a salt dissolves, the metal ions in the salt solution react with/bond to water molecules to forms aquo complex ions. Example: CuSO 4 (s) Cu 2+ (aq) + SO 4 2- (aq) [Cu( 2 O) 4 ] 2+ Examples [( 2 O)] + ydronium ion [Pb( 2 O) 4 ] 2+ Tetra aquo lead ion [Cu( 2 O) 4 ] 2+ Tetra aquo copper(ii)ion [Ni( 2 O) 6 ] 2+ exa aquo nickel ion Colored aquo complex ions contain a transition metal ion with incompletely filled d orbitals. Part 1. Acidity of Cations Study the reaction of metal aquo complex ions with the Lewis base 2 O to produce hydronium ions. Collect p data for different metal aquo complex ions in aqueous solution. p versus periodic table position of ion s metal? p versus metal ion size and charge? extent of s Metal Ion Acid Strength + M x+... O + The acid strength of a metal ion is dependent on its ability to attract electrons (oxidizing agent strength) The greater the acid strength of a metal ion the more polarized the bonded water molecules (and electron deficient the protons) in the aquo complex ion. 3

4 Reactions of Metal Aquo Complex Ions with Water Reaction of Metal Aquo Complex Ion: Q. Complete a balanced equation to show formation of hydronium ions: [Al ( 2 O) 6 ] O [Al( 2 O) 5 (O)] 2+ + [- 2 O] + Electron deficient proton/s in the polarized water molecules of the metal aquo complex ion react and bond to an electron pair in another water molecule [Al( + 2 [ 3 O] + 2 O) 6 ] O [Al( 2 O) 4 (O) 2 ] + When a proton bonds to a water molecule, a 3 O + ion is formed. Metal Ion Acid Strength Q. Given the reducing agent strength Na > Mg > Al, indicate the Lewis acid strength of Na +, Mg 2+, and Al 3+ Metal Ion Acid Strength: Al 3+ > Mg 2+ > Na + 1A 1 1s1 IIA IIIA IVA VA VIA VIIA 3 Li 2s Na 3s K 4s Rb 5s Cs 6s Fr 7s 1 4 Be 2s Mg 3s2 IIIB IVB VB VIB VIIB VIIIB! VIIIB IB IIB 2 0 Ca 4s Sr 5s 2 Aquo Complex Ion Reactions Acid strength Sc Ti V Cr Mn Fe Co Ni 3d 1 4s 2 3d 2 4s 2 3d 3 4s 2 3d 5 4s 1 3d 5 4s 2 3d 6 4s 2 3d 7 4s 2 3d 8 4s Y Zr Nb Mo Tc Ru Rh Pd 4d 1 5s 2 4d 2 5s 2 4d 3 5s 2 4d 5 5s 1 4d 5 5s 2 4d 7 5s 1 4d 8 5s 1 4d 10 VIIIA 2 e 1s B C N O F Ne 2s 2 2p 1 2s 2 2p 2 2s 2 2p 3 2s 2 2p 4 2s 2 2p 5 2s 2 2p Al Si P S Cl Ar 3s 2 3p 1 3s 2 3p 2 3s 2 3p 3 3s 2 3p 4 3s 2 3p 5 3s 2 3p Cu Zn Ga Ge As Se Br Kr 3d 1 0 4s 1 3d 1 0 4s 2 4s 2 4p 1 4s 2 4p 2 4s 2 4p 3 4s 2 4p 4 4s 2 4p 5 4s 2 4p Ag Cd In Sn Sb Te I Xe 4d 1 0 5s 1 4d 1 0 5s 2 5s 2 5p 1 5s 2 5p 2 5s 2 5p 3 5s 2 5p 4 5s 2 5p 5 5s 2 5p Ba La* f 7 3 Ta 7 4 W 7 5 Re 7 6 Os 7 7 Ir 7 8 Pt 7 9 Au 8 0 g 8 1 Tl 8 2 Pb 8 3 Bi 8 4 Po 8 5 At 8 6 Rn 6s 2 5d 1 6s 2 5d 6s 5d 6s 5d 6s 5d 6s 5d 6s 2 5d 6s 2 5d 6s 6s 6p 6s 2 6p 2 6s 2 6p 3 6s 2 6p 4 6s 2 6p 5 6s 2 6p d 1 0 6s 1 5d 1 0 6s Element synthesized, Ra Ac # but no official name assigned 7s 2 6d 1 7s 2 6d 2 7s 2 6d 3 7s 2 6d 4 7s 2 6d 5 7s 2 6d 6 7s 2 6d 7 7s 2 4

5 Part 2 A. Studies of complex formation with N 3 and O -. Study the reactions of metal aquo complex ions with Lewis bases (N 3, O -, ). DISCUSSION What kinds of observations allow you to infer that a complexation reaction is occurring? Predict the reactions of a metal ion with Lewis bases based on the position of its element in the Periodic Table 1A 1 1s1 IIA IIIA IVA VA VIA VIIA 3 Li 2s Na 3s K 4s Rb 5s Cs 6s Fr 7s 1 4 Be 2s Mg 3s2 IIIB IVB VB VIB VIIB VIIIB! VIIIB IB IIB 2 0 Ca 4s Sr 5s 2 Reaction of Lewis Acids (metal ions) with Lewis Bases Extent of reaction differs because of acid strength differences. Pattern of reactivity with bases (e.g. O - and N 3 ) differs due to differences in metal ion electron configurations Sc Ti V Cr Mn Fe Co Ni 3d 1 4s 2 3d 2 4s 2 3d 3 4s 2 3d 5 4s 1 3d 5 4s 2 3d 6 4s 2 3d 7 4s 2 3d 8 4s Y Zr Nb Mo Tc Ru Rh Pd 4d 1 5s 2 4d 2 5s 2 4d 3 5s 2 4d 5 5s 1 4d 5 5s 2 4d 7 5s 1 4d 8 5s 1 4d 10 VIIIA 2 e 1s B C N O F Ne 2s 2 2p 1 2s 2 2p 2 2s 2 2p 3 2s 2 2p 4 2s 2 2p 5 2s 2 2p Al Si P S Cl Ar 3s 2 3p 1 3s 2 3p 2 3s 2 3p 3 3s 2 3p 4 3s 2 3p 5 3s 2 3p Cu Zn Ga Ge As Se Br Kr 3d 1 0 4s 1 3d 1 0 4s 2 4s 2 4p 1 4s 2 4p 2 4s 2 4p 3 4s 2 4p 4 4s 2 4p 5 4s 2 4p Ag Cd In Sn Sb Te I Xe 4d 1 0 5s 1 4d 1 0 5s 2 5s 2 5p 1 5s 2 5p 2 5s 2 5p 3 5s 2 5p 4 5s 2 5p 5 5s 2 5p Ba La* f 7 3 Ta 7 4 W 7 5 Re 7 6 Os 7 7 Ir 7 8 Pt 7 9 Au 8 0 g 8 1 Tl 8 2 Pb 8 3 Bi 8 4 Po 8 5 At 8 6 Rn 6s 2 5d 1 6s 2 5d 6s 2 5d 6s 2 5d 6s 2 5d 6s 2 5d 6s 2 5d 6s 2 5d 6s 6s 6p 6s 2 6p 2 6s 2 6p 3 6s 2 6p 4 6s 2 6p 5 6s 2 6p d 1 0 6s 1 5d 1 0 6s Element synthesized, Ra Ac # but no official name assigned 7s 2 6d 1 7s 2 6d 2 7s 2 6d 3 7s 2 6d 4 7s 2 6d 5 7s 2 6d 6 7s 2 6d 7 7s 2 Metal Aquo Complex Ion Reactions with O - Aquo Complex Ion Reactions with O - If reaction occurs with a charged base such as O -, the product may be a soluble complex ion or an uncharged insoluble complex depending on reaction stoichiometry. Example 2: Formation of a insoluble complex: [Al ( 2 O) 6 ] O - [Al( 2 O) 3 (O) 3 ] O Example 1: Formation of a soluble complex ion: [Al ( 2 O) 6 ] 3+ + O - [Al( 2 O) 5 (O)] O Traditional net precipitation equation: Al 3+ (aq) + 3O - (aq) Al(O) 3 (s) 5

6 Aquo Complex Ion Reactions with O - Example 3: Addition of excess hydroxide ions to the precipitated hydroxide complex results in formation of a soluble complex ion: [Al ( 2 O) 3 (O) 3 ] + 3O - [Al(O) 6 ] O Addition of Base (NaO ) [Al( 2 O) 6 ] 3+ [Al( 2 O) 5 (O)] 2+ [Al( 2 O) 4 (O) 2 ] + [Al( 2 O) 3 (O) 3 ] [Al( 2 O) 2 (O) 4 ] - [Al( 2 O) (O) 5 ] 2- [Al(O) 6 ] 3- Precipitation reactions are Lewis Acid-Base reactions The reactions are reversible equilibrium systems The equilibrium point depends on the reactants (strength ) and reaction conditions (concentration ) Addition of acid (+) Reaction of Aquo Metal Complex Ions with N 3 If a precipitate forms upon addition of N 3 (aq), the metal aquo complex ion is reacting with the SMALL AMOUNT of O - ions present in N 3 (aq): N 3 (aq) + O(l) N + 4 (aq) + O - (aq) Lewis acids bond to the best available base. - an acid does not react (bond) to any base. Wanna give me a try? [Cu( 2 O) 4 ] 2+ + N 3 light blue precipitate* Q. * What is the formula for the hydroxide precipitate? [Cu( 2 O) 2 (O) 2 ] (s) Acid-Base + Base no reaction 6

7 If a better base is available a Lewis acid will react (exchange partners)! Q. The acid exchanging base partners is +. Which is the BEST base, Cl - or O? Cl- + O Cl - + O Acid Base Base Acid Acid-Base + better Base Reaction + bonds to water (best base) rather than Cl -. The bonded base-acid product = complex ion. Aquo Complex Ion Replacement Reactions Example 1: Replacement of water with ammonia molecules. Aquo Complex Ion Reactions Example: Replacement of water with ammonia molecules. [Cu ( 2 O) 4 ] N 3 [Cu(N 3 ) 4 ] O Tetra aquo Cu(II) ion Tetra ammine Cu(II) ion [Cu(N 3 ) 4 ] 2+ Tetrammine copper (II) ion 7

8 Complex Ions Aquo Complex Ion Reactions Colored transition metal ions alter color upon bonding to a different Lewis base. Complex ions are the chemical basis for colorful paint pigments. [Cu( 2 O) 4 ] 2+ [Cu(N 3 ) 4 ] 2+ The charge on a complex ion will equal that of the metal ion when the metal ion is bonded to an uncharged Lewis base such as 2 O or N 3. Aquo Complex Ion Replacements Reactions Example 2: Replacement of water with chloride ions. Q. Complete the equation below: [Cu ( 2 O) 4 ] Cl - [Cu(Cl) 4 ] O Lewis Acid-Base Reactions Complexes react if a better partner (acid or base) is available so as to form a more stable bond. Tetra aquo copper(ii) ion Tetra chloro copper(ii) ion The charge on the complex ion alters due to reaction with a charged Lewis base emoglobin is a complex of Fe that binds to/transports oxygen 8

9 Aquo Complex Ion Replacement Reactions Example 4: The base ammonia in the Cu(II) product (ammine complex ion) will react and bond to a better acid than Cu(II) ions such as + : [Cu ( 2 O) 4 ] N 3 [Cu(N 3 ) 4 ] O Questions? Contact Q. What will you observe upon adding acid ( + ) to the deep violet-blue ammine product? 9

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1s 1. [He]2s 1. [He]2s 2. [He]2s 2 2p 2. [He]2s 2 2p 1. [He]2s 2 2p 4. [He]2s 2 2p 3. [He]2s 2 2p 6. [He]2s 2 2p 5

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