Lecture 18 Acids and Bases

The Second Exam (Thursday) The Focus will be upon the material covered since the last exam, but material prior to that may also be examined. So study all your notes. I will pick up the student assignments from the front office at 4 pm on Friday. Assignments received at the front office after this will be considered late. ----------------Student Lecture Tuesday 21st April Tyler Lily Steve Ana Jesse Julie Tomas Matt Danielle Nicole Devon Ashley

Thursday 23rd April Tuesday 28th April

Determine when you wish to present, remember there are only limited slots, and no make up sessions are allowed. --------------------------Student Lectures are to be 25 minutes long (shorter presentations will lose points), with 5 minutes for question from the class (also worth points). A handout will be given to each member of the audience before the start of each lecture, to be filled out during the student lecture. This is assessable. This is not an excuse to goof off, the student lectures are as much a part of the class as the regular lectures. Absences from the other lectures will be penalized. ----------------------------------Review session Thursday 30th April Final Exam 7:30 am 9:30 am Tuesday 5th May

Please remember that 50% of your assessment is still to come.

Inorganic Chemistry CHM450

What are the Learning Objectives of the CHM450 Lecture Course?

The objectives of this class are to: 1) Give a deeper understanding of inorganic chemistry and to demonstrate the relationship between inorganic chemistry and other chemical disciplines. 2) Introduce you to important concepts in inorganic chemistry including: i) Nuclear chemistry, including fission, fusion and other topics. ii) The relationship between inorganic and physical/quantum chemistry iii) The structure of orbitals, with a focus of the d, f and higher orbitals. iv) The utility of symmetry and group theory for predicting molecular vibrations, sigma and pi bonding contributions, and orbital hybridization. v) An understanding of molecular orbital theory. vi) Advanced aspects of acids and bases, including HSAB theory. vii) The crystalline solid state including unit cells and basic crystallography. vii) Band theory, conductivity and superconductivity. 3) Demonstrate your understanding of the above topics, by giving a major presentation to the class on a topic related to inorganic chemistry.

CHEM450 Student Lecture - Outline for the Presentation

Topic:

You must show me your presentation before you give it to the lecture. For those in CHM450L, this will be during the lab period on Wednesday 16th April. If your presentation is not sufficiently ready, I will not allow you to present.

Time:

The presentation must be 25 minutes long, points will be deducted for being over or under this time limit. It is essential that you practice this seminar beforehand, as you will inevitably rush through your presentation.

Format:

The presentation must be in power point format, a computer and projector will be available. I would suggest brining your own computer, but also bring your file in a minimum of two formats i.e. USB key and CD-ROM.

Content:

Focus your presentation on the inorganic chemistry. Presentations that fail to do this will be marked down. Break the report into smaller sections with a heading. Begin your presentation with a logical outline of what you intend to discuss.

References:

Use Cline Library to obtain a minimum of six hard-copy literature references, do not list internet references. You must show how your hard-copy references relate to the material described. Use the ACS referencing style. If you do not know what this is, consult with someone who does before you submit your written assignment. Do not cite Wikipedia! I will check your references.

Lecture 18 Acids and Bases The Many Different Ways of Classifying Acids and Bases Arrehius Concept Arrhenius acids form hydronium ions (H3O+) in aqueous solution Arrhenius bases form hydroxide ions (OH-) in aqueous solution

Lowry-Brnsted Concept An acid is a species with a tendency to lose a hydrogen ion. A base is a species with a tendency to gain a hydrogen ion.

Solvent System Concept Solvent dissociation leads to an acid (cation) and a base (anion). A solute that increases the concentration of the cation is an acid. A solute that increases the concentration of the anion is a base.

Lewis Concept A Lewis acid is an electron pair acceptor. A Lewis base is an electron pair donor.

Lewis expanded the definitions of acids and bases to include non-protic, non-hydroxide systems The growth of chemical investigations in nonaqueous and mixed-solvent media has increased the importance of considering acid-base behavior in the absence of water

Lecture 18 Acids and Bases Homework Question from pg 204 (M and T) Problem 6-1 to 6-7 For each of the following reactions, identify which acid-base definition applies (Lewis, Solvent System or Lowry-Bronsted).

Lewis, Solvent system

Lewis, Lowry-Bronsted

Lewis, solvent system

Lewis, solvent system

Lewis

Lewis

Lewis

Lewis, solvent system

Lecture 18 Acids and Bases Hard-Soft Acid-Base Concept A Lewis acid is an electron pair acceptor. A Lewis base is an electron pair donor. Example: Metal ions Example: Inorganic anions

Hard

Small, highly charged ions. Base example: F- and OAcid example: Al3+ and Mg2+

Soft

Large, easily polarized ions. Base example: I- and Te Acid example: Pb2+ and Hg2+

Hard Lewis acids tend to combine with hard Lewis bases, and soft Lewis acids tend to combine with soft Lewis bases

The important properties to consider in the classification of Lewis acids and bases are electronegativity, size and charge.

Lecture 18 Acids and Bases It is important to be able to distinguish hard and soft acids and bases.

Lecture 18 The Characteristics of Hard and Soft Acids and Bases Soft Acids Heavy metal ions Insoluble chlorides Chemically inert Fairly electronegative (1.9 - 2.54) Large size (> 90 pm) Low charge (+1 or +2)

Hard Acids Most group 1 and 2 metals Electronegativity between 0.7 and 1.6 Small (<90 pm) Often highly charged (3+ or higher)

Soft Bases C, P, As, S, Se, Te, Br, I donor atoms Electronegativity between 2.1 and 2.96 Radius > 170 pm

Hard Bases O, F donor atoms Very high electronegativity Radius ~ 120 pm Examples are sulfate, carbonate, silicate, acetate, alcohols, ketones

Lecture 18 The Characteristics of Hard and Soft Acids and Bases

Relative Softness The relative softness of soft acids can be estimated from the distance of the acid from Au, the softest atoms. For 1st row metals, the 2+ state is borderline, the 3+ state is clearly hard and the 1+ state (only observed for traditional coordination complexes as Cu(I)) is soft.

Acids get softer as they get heavier.

The softest bases are those with the lowest electronegativity and lie along the metal-nonmetal border.

Donor atom softness is also influenced by the substituent atoms in bases like phosphines and arsine.

Example: Which phosphine is softer?

PH3 vs. PF3

PH3 is a softer base. In PF3 the electronegative fluorine atoms are removing electron density from the lone pair. This is the inductive effect.

Inductive effect:

As substituents become more electronegative, they remove electron density from the central atom, and the lone pair is less readily donated to an acid.

Lecture 18 Hard and Soft Acids and Bases (Pg 183) What Does HSAB Theory Tell Us? 1) Solubilities of Common Complexes.

Soft-Soft and Hard-Hard complexes are likely to be insoluble. Soft-Hard complexes will be more soluble.

This influences the natural occurrence of many minerals. Example: In nature, is Be2+ more likely to occur in combination with sulphur (soft base) or with oxygen (hard base)? Be2+ occurs almost exclusively in nature as an aluminosilicate with the formulae Be3Al2(SiO3)6. This is the mineral known as beryl.

Lecture 18 Hard and Soft Acids and Bases

2) Predicting Reaction Direction

Nb2S5 + 5 HgO Nb2O5 + 5 HgS

What will be the preferred direction of the above reaction?

Cation Type Nb5+ Hg2+ hard

Why High electronegativity and charge

soft Low electronegativity and charge; closer to Au

Anions S2O2-

Type soft Hard

Why Lower electronegativity, large High electronegativity, small

Therefore, products are favored since they match a hard acid with a hard base and a soft acid with a soft base.

Predict the direction of the following reaction, justify your answer

AgF + 2NH3 [Ag(NH3)2]+ + FThe direction proceeds to favour [Ag(NH3)2]+ + F- because [Ag(NH3)2]+ is an example of a soft-soft interaction.
This can be used to dissolve insoluble silver halides.

Lecture 18 Hard and Soft Acids and Bases 3) Size of the HOMO-LUMO Gap Softsoft combinations depend mainly on covalent bonding and hardhard combinations mainly on ionic bonding. Generally, hard molecules are those with large HOMO-LUMO gaps, and soft molecules are those with small HOMO-LUMO gaps. Softsoft combinations depend mainly on covalent bonding and hardhard combinations mainly on ionic bonding. A smaller HOMO-LUMO gap means greater covalent bonding, and hence lower solubility in water and increased colour (due to absorption in the visible part of the spectrum).

Lecture 18 Hard and Soft Acids and Bases

Do atoms become harder or softer as you move down a column of the periodic table? What effect will this have on the HOMO-LUMO gap? It will become smaller, there will be greater sharing of electrons and the bond will become more covalent.

Lecture 18 Hard and Soft Acids and Bases We have seen previously that HF is composed of two orbitals (s on the H (-13.6 eV), and pz on the F(-18.65 eV)) that are polarized due to their differences in energy. H+ is soft and F- is hard. (Hard-soft interaction is less favourable) As we go down the periodic table, the interaction becomes more favourable (soft-soft)

In aqueous solutions, acidity increases (decreasing pKa) pKa of HF = 3.15 pKa of HCl = -7 pKa of HBr = -9 pKa of HI = -10

Hard-hard interactions may be considered to be primarily electrostatic interactions (ionic), with little change in the energies of the HOMO and LUMO orbitals. Soft-soft interactions involve orbitals that are typically closer together resulting in a large change in the HOMO/LUMO orbital energies and more even sharing of electrons (covalent bond).

HF is an unusual case as in aqueous solution it dissociates to form tightly bound F-H3O+. In more concentrated solutions it undergoes the auto-dissociation reaction 2HF H+ + FHF-

Lecture 18 The Effect of Electronegativity on Acids and Bases (pg 196)

We saw that as the electronegativity increases around the lone pair donor, the base becomes weaker.

What happens when the electronegativity increases on an acid?

The acid becomes stronger.

Compare H2SO3 and H2SO4, which is the stronger acid? H2SO4 (sulfuric acid) is much stronger than H2SO3 (sulfurous acid)

This is because the additional oxygen atoms withdraw electron density from the central atom making the central atom more positive. This weakens the O-H bond, making it easier for the acid to donate H+.

The reverse applies to bases.

pKa 9 7n
Where n is the number of nonhydrogenated oxygen atoms per molecule

For some acids, [pKa = 8 5n] fits better, but we will stay with the above.

Lecture 18 The Effect of Electronegativity on Acids and Bases

Predict the pKa for the following acids HClO4 HClO3 HClO2 HOCl

Use pKa 9 7n and pKa 8 5n

Lecture 18 Super-Acids Super-Acid: Any acid more acid than concentrated sulphuric acid. The acidity is determined using p-nitroaniline

HF: Hydrogen Fluoride Actually the weakest hydrogen halide in aqueous solution Strong hydrogen bonding gives the tightly bound complex H3O+FExtremely toxic. Reacts with Ca2+ to give insoluble CaF2 in the body.

Antimony Pentafluoride The conversion from SbF5 to [SbF6]- is strongly favoured This leaves a naked proton, since [SbF6]- is non-coordinating. Fluoroantimonic acid is 21019 times stronger than 100% sulfuric acid. Fluoroantimonic acid will protonate alkanes: MeC4 + H+ MeC3+ + CH4

Lecture 18 Super-Acids (Hydrofluoric Acid)

Dont be this person!

Lecture 18 Super-Bases Hydroxide (OH-) is the strongest base that can occur in aqueous solution. Stronger bases deprotonate water to give the hydroxide ion The powerful Lochmann-Schlosser base is a combination of tert-butyl lithium and sodium methoxide.

Other superbases include the Proton Sponge family of compounds.

These proton chelators lead to a dramatic increase in basicity on account of the following: (i) destabilization of the initial base as a consequence of strong repulsion of the unshared electron pairs; (ii) formation of an intramolecular hydrogen bond (IHB) in the protonated form; and (iii) relief of the steric strain upon protonation in the final state.

Lecture 18 Homework Problems

Exercises 6-1, 6-2, 6-4, 6-8

Problems 6-1, 6-2, 6-3, 6-4, 6-5, 6-6, 6-7, 6-10, 6-13, 6-14, 6-15, 6-23, 6-28, 6-30

Lecture 18 The Crystalline Solid State (Chapter 7)

The Idea of the Unit Cell

Unit Cell: The smallest repeating array of atoms in a crystal.
This matters because minerals, metals and many other types of material in the universe occur as crystalline solids. If a material is not crystalline, it is amorphous.

Amorphous Solid: A material with random arrangement of atoms or molecules. A material with no long-range order. Examples: Paraffin wax, polystyrene, etc