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November 5 - 11
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
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
DEMO DEMO
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
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)
3
Part 2. Complexation Reactions
Q. Complete a balanced equation to show formation
of hydronium ions:
The reaction of a Lewis acid with a Lewis base
(NH3, OH-, ).
[Al(H2O)6]3+ + 2 HOH Data Analysis
What kinds of observations allow you to know
that a complexation reaction is occurring?
[Al(H2O)4(OH)2]+ + 2 [H3O]+
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?
Metal Aquo Complex Ion Reactions Metal Aquo Complex Ion Reactions
If reaction occurs with a charged Lewis base Formation of an insoluble complex:
such as OH-, the product may be a soluble
complex ion or an uncharged insoluble complex. [Al (H2O)6]3+ + 3OH- [Al(H2O)3(OH)3] + 3H2O
Formation of a soluble complex ion:
4
Metal Aquo Complex Ion Reactions Lewis Acid-Base Reactions
Addition of excess hydroxide ions to the Note that water molecules in the metal ion
precipitated hydroxide complex results in the aquo complex are replaced with OH- ions
formation of a soluble complex ion:
[Al (H2O)6] + 6 OH- [Al(OH)6]3- + 6 H 2O
[Al (H2O)3(OH)3] + 3OH- [Al(OH)6]3- + 3 H 2O
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-
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.
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
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
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+
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.
DEMO
Addition of NH 3 to Cu 2+
resulting in a copper [Cu(H2O)4]2+ [Cu(NH3)4]2+
hydroxide ppt.
[Cu(H2O)4]2+ [Cu(NH3)4]2+
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
7
Questions?
Contact nkerner@umich.edu