E5 Lewis Acids and Bases (Session 1) Acids

November 5 - 11

Session one Bronsted: Acids are proton donors.

Pre-lab (p.151) due
Problem
1st hour discussion of E4 Compounds containing cations other than
Lab (Parts 1and 2A) H+ are acids!

Session two
DEMO
Lab: Parts 2B, 3 and 4

Problem: Some acids do not contain protons Lewis Acids and Bases

Example: Al3+ (aq) = pH 3! Defines acid/base without using the word proton:
H H H +

Cl-H + O
Cl- O
H H

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

Lewis Acids Lewis Bases

Electron rich species; electron pair donors.
Electron deficient species ; potential electron
pair acceptors.
Lewis acids: H+ Cu2+ Al3+

Im deficient! Ammonia hydroxide ion water__

(ammine) (hydroxo) (aquo)

Acid

1
 Lewis Acid-Base Reactions Lewis Acid-Base Reactions

Example
Metal ion
H H H + BONDED
H+ +

O to water
O molecules
H H
Metal ion
Acid + Base Complex ion surrounded
by water
The acid reacts with the base by bonding to one molecules
or more available electron pairs on the base.
The acid-base bond is coordinate covalent.
The product is a complex or complex ion

Lewis Acid-Base Reaction Products Lewis Acid-Base Reaction Products

Net Reaction Examples Net Reaction Examples

Pb2+ + 4 H2O [Pb(H2O)4]2+ H+ + H2O [H(H2O)]+

Lewis acid Lewis base Tetra aquo lead ion Lewis acid Lewis base Hydronium ion

Ni2+ + 6 H2O [Ni(H2O)6]2+ Cu2+ + 4 H 2O [Cu(H2O)4]2+

Lewis acid Lewis base Hexa aquo nickel ion Lewis acid Lewis base Tetra aquo copper(II)ion

DEMO DEMO

Metal Aquo Complex Ions Part 1. Acidity of Cations

The metal ions in a salt solution bond to water
molecules to forms aquo complex ions. Compare the pH of nitrate salts containing different
metal ions.
Example:
EXPERIMENT VARIABLE
Cu2+(aq) + SO42- (aq)
Nitrate salts with different metal ions
EXPERIMENT CONSTANT
[Cu(H2O)4]2+
Water to dissolve salts is from same source and of
constant pH (neutral or non-acidic).
Hydrated solid:
DEMO
[Cu(H20)4]SO4 DEMO
pH of Na+, Mg2+, and Al3+
tetra aquo copper(II) sufate

2
 Metal Ion Acidity
Metal Ion Acid Strength
Acid strength
Al3+
> Mg2+
> Na+
Metal Ion Acid Strength: ___________________ 1A Oxidizing agent strength VIIIA
1 2
H He
1 s1 IIA IIIA IVA VA VIA VIIA 1 s2
Results suggest that metal ion acidity and 3 4 5 6 7 8 9 10
Li Be B C N O F Ne
metal ion charge are linked 2s1 2s2 2 s 2 2 p1 2 s 2 2 p2 2 s 2 2 p3 2 s 2 2 p4 2 s 2 2 p5 2 s 2 2 p6
11 12 13 14 15 16 17 18
Na Mg Al Si P S Cl Ar
Results suggest that metal ion acidity and 3s1 3s2 IIIB IVB VB VIB VIIB VIIIB VIIIB IB IIB 3 s 2 3 p1 3 s 2 3 p2 3 s 2 3 p3 3 s 2 3 p4 3 s 2 3 p5 3 s 2 3 p6
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
metal ion oxidizing agent strength are linked K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn
10 1 10 2
Ga Ge As Se Br Kr
4s1 4s2 3d1 4 s2 3d2 4 s2 3d3 4 s2 3d5 4 s1 3d5 4 s2 3d6 4 s2 3d7 4 s2 3d8 4 s2 3d 4s 3d 4s 4 s2 4 p14 s2 4 p2 4 s2 4 p3 4 s2 4 p4 4 s2 4 p5 4 s2 4 p6
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
10 1 10 2
5s1 5s2 4d1 5 s2 4d2 5 s2 4d3 5 s2 4d5 5 s1 4d5 5 s2 4d7 5 s1 4d8 5 s1 4d1 0 4d 5s 4d 5s 5 s2 5 p1 5 s2 5 p2 5 s2 5 p3 5 s2 5 p4 5 s2 5 p5 5 s2 5 p6
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Cs Ba La* Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
10 1 10 2
6s1 6s2 5d1 6 s2 5d2 6 s2 5d3 6 s2 5d4 6 s2 5d5 6 s2 5d6 6 s2 5d7 6 s2 5d9 6 s1 5d 6s 5d 6s 6 s2 6 p1 6 s2 6 p2 6 s2 6 p3 6 s2 6 p4 6 s2 6 p5 6 s2 6 p6
87 88 8 9 1 0 4 1 0 5 1 0 6 1 0 7 1 0 8 1 0 9 + Element synthesized,
Fr Ra Ac# + + + + + + but no official name assigned
7s1 7s2 6d1 7 s2 6d2 7 s2 6d3 7 s2 6d4 7 s2 6d5 7 s2 6d6 7 s2 6d7 7 s2

Acidity of Metal Ions Acidity of Metal Ion Model

Reminder: H+
Metal ions x+ ..
BOND
M .. O
to electron H+
pairs on Metal ion acid strength is related to its ability to
water
molecules! attract and bond to electrons (oxidizing agent strength)

When a metal ion bonds to a water molecule, the

water molecules polarity increases and the protons in
the water molecule become more electron deficient

Acidity of Metal Ion Model Q. Complete a balanced equation to show formation

of hydronium ions:
Equation describing acidity of metal ions:

[X(H2O)6]2+ + H2O [X(H2O)5(OH)]+ + [H-H2O]+ [Al(H2O)6]3+ + HOH

Electron deficient proton/s in the bonded water [Al(H2O)5(OH)]2+ + [H3O]+

molecule (of the metal aquo complex ion) are
donated(bond) to an external water molecule

When protons bond to water molecules, H3O+

ions are formed producing a pH drop.

3

Q. Complete a balanced equation to show formation
of hydronium ions:
[Al(H2O)6]3+ + 2 HOH
[Al(H2O)4(OH)2]+ + 2 [H3O]+
Part 2 Lewis Acid-Base Reactions
Lewis acids
Metal aquo complex ions
Formula for metal aquo complex ion is provided
Lewis bases
OH- (NaOH)
NH3
Metal Aquo Complex Ion Reactions
If reaction occurs with a charged Lewis base
such as OH-, the product may be a soluble
complex ion or an uncharged insoluble complex.
Formation of a soluble complex ion:
[Al (H2O)6]3+ + OH- [Al(H2O)5(OH)]2+ + H2O
Part 2. Complexation Reactions
The reaction of a Lewis acid with a Lewis base
(NH3, OH-, ).
Data Analysis
What kinds of observations allow you to know
that a complexation reaction is occurring?
Are Lewis acid-base reaction results predictable
from a) metal ion acid strength? b) the position of
the metal ions element in the Periodic Table?
Part 2 Lewis Acid-Base Reactions
Example
Al exists as [Al(H2O)6]3+
Add NaOH
DEMO
Metal Aquo Complex Ion Reactions
Formation of an insoluble complex:
[Al (H2O)6]3+ + 3OH- [Al(H2O)3(OH)3] + 3H2O
Precipitation reactions are Lewis acid-base reactions!
Traditional net precipitation equation:
Al 3+(aq) + 3OH- (aq) Al(OH)3 (s)
4
 Metal Aquo Complex Ion Reactions Lewis Acid-Base Reactions

Addition of excess hydroxide ions to the
precipitated hydroxide complex results in the
formation of a soluble complex ion:
[Al (H2O)3(OH)3] + 3OH- [Al(OH)6]3- + 3 H 2O
Note that water molecules in the metal ion
aquo complex are replaced with OH- ions
[Al (H2O)6] + 6 OH- [Al(OH)6]3- + 6 H 2O

1:1 1:2 1:3 1:4 1:5 1: 6

Stoichiometry of Reaction Products: Al3+ to OH-

[Al(H2O) 6]3+ Lewis acids bond to the best available

Addition of Base (NaOH)

base. - an acid does not react (bond) to any base.
Addition of acid (H+)

[Al(H 2O)5(OH)] 2+

[Al(H 2O)4(OH) 2] +
Wanna give me a try?
[Al(H2O)3(OH) 3]

[Al(H2O)2(OH) 4]-

[Al(H2O) (OH) 5] 2-

[Al(OH)6]3-

Lewis Acid-Base reactions are reversible

Acid-Base + Base no reaction
equilibrium systems

If a better base is available a Lewis acid will Lewis Acid-Base Replacement Reactions
react (exchange partners)!
Complexes react if a better partner (acid or base)
is available so as to form a more stable bond.

Acid-Base + better Base Reaction

Hemoglobin is a complex of Fe that binds to/transports oxygen

5
Q. The acid exchanging base partners is H+. Aquo Complex Ion Replacement Reactions
Which is the BEST base, Cl- or HOH?
Example:
Replacement of water molecules in [Cu (H2O)4]2+
H H H + with ammonia molecules.

Cl-H + O Cl- O

H H
[Cu (H2O)4]2++ 4 NH3 [Cu(NH3)4]2+ + 4 H2O

Acid Base Base Acid

DEMO

H+ bonds to water (best base) rather than Cl-.

The bonded base-acid product = complex ion. Tetra aquo Cu(II) ion Tetra ammine Cu(II) ion

Aquo Complex Ion Replacement Reactions Aquo Complex Ion Replacement Reactions
Example:
Net reaction:
Replacement of water molecules in [Cu (H2O)4]2+
with ammonia molecules.
[Cu(H2O)4]2++ 4 NH3 [Cu(NH3)4]2+ + 4 H2O

[Cu (H2O)4]2++ 4 NH3 [Cu(NH3)4]2+ + 4 H2O

DEMO
[Cu(H2O)4 ](NO 3)2 + 4 NH3 [Cu(NH3)4](NO 3)2 + 4 H 2O
Tetra aquo Cu(II) nitrate Tetra ammine Cu(II)nitrate
Tetra aquo Cu(II) ion Tetra ammine Cu(II) ion

Aquo Complex Ion Replacement Reactions Aquo Complex Ion Replacement Reactions

The base NH 3 bonded to Cu2+ in [Cu(NH3)4]2+ will [Cu(H2O)4]2++ 4 NH3 [Cu(NH3)4]2+ + 4 H2O
exchange partners if a better Lewis acid than Cu(II)
ions are available. +
H+

DEMO: Addition of H+ NH4+

[Cu(NH3)4]2+ Upon addition of H+, NH3 bonds to H+ (rather

than Cu2+).
Cu2+ re-bonds to H2O.

6
 Reactions with NH3 Aquo Complex Ion Reactions
If a precipitate forms upon addition of NH3(aq), the
metal aquo complex ion is reacting with the SMALL Coloredtransition metal complex ions alter
AMOUNT of OH- ions present in NH3(aq): color upon bonding to a different Lewis base.

NH3(aq) + HOH(l) NH4+ (aq) + OH- (aq)

DEMO
Addition of NH 3 to Cu 2+
resulting in a copper [Cu(H2O)4]2+ [Cu(NH3)4]2+
hydroxide ppt.

[Cu(H 2O) 4]2+ + 2 OH- [Cu (H 2O)2(OH)2] + 2 H 2O

Complex Ions Aquo Complex Ion Reactions

[Cu(H2O)4]2+ [Cu(NH3)4]2+

The charge on a aquo metal complex ion

Complex ions are the chemical basis for will = the metal ion charge if the bonded
colorful paint pigments. Lewis base is uncharged (e.g., H2O or NH3)

Aquo Complex Ion Replacement Reactions Aquo Complex Ion Replacement Reactions
Example: Q. Complete the equation below:
Replacement of neutral water molecules in [Cu(H2O)4]2+
with a charged Lewis base - chloride ions. [Cu (H2O)4]2+ + 4 Cl- [Cu(Cl) 2- + 4 H O
4]
___________________2

DEMO

The charge on the complex ion alters due to

[Cu(H2O)4]2+ [Cu(Cl)4]2- replacement of a neutral Lewis base (water) with a
charged Lewis base

7
 Questions?
Contact nkerner@umich.edu