Brian Wong

Ch 24 Self-Notes

1. Host crystal affects atomic orbitals in transition metals. Atoms in the crystal
creaqte a field around the ion called the crystal field that splits the five
normally degenerate d orbitals in two or more levels. The color of the
gemstone is caused by electron transitions between these levels.
2. Differences in crystal color depend on energy differences between orbitals
involved in absorption.
3. Properties of Transition Metals
• Moderate to High Density
• Good Electric Conductivity
• High Melting Point
• Moderate to Extreme Hardness
• Have electrons in do orbitals that can be involved in metallic bonding
• Unique and exhibit a wide variety of chemical behavior
1. As you move right across a row of transition elements, electrons are added to
the (n-1)d orbitals, where n is the row number/quantum number of the
highest occupied principle level
2. 3rd and 4th row of transition metals ground state electron configuration is
[noble gas]ns2(n-1)dx
3. Little difference in atomic size (radius) of transition metals across a row
except for the 1st and 2nd
4. Third Row of Transition Metals are not much larger than the 2nd Row of
Transition metals because of the 14 electrons that have gone to the f orbitals
that are lower in principal quantum levels and ineffective at shielding the
outer electrons from nuclear charge. Also, outer electrons are held more
tightly by the nucleus, making the 3rd row of transition metals smaller than
expected.- Lanthanide Contraction
5. First Ionization energy slowly increases across a row, but slowly compared to
the rate of increase for main-group elements. In the transition elements the
charge of the nucleus increases substantially from one row to the next.
6. Electronegativity slowly increases across a row, but slower than main-group
elements. Electronegativity generally increases from the 1st to 2nd rows, but
no increase is seen from the 2nd to 3rd row. This is different from the main-
group elements because the main group elements decrease in
electronegativity as row number increases because of the relatively small
change in atomic size moving from one column to another for transition
elements, with a large increase in nuclear charge. Gold is the most
electronegative transition metal.
7. Transition Metals exhibit a variety of oxidation states, the highest being +7
for Mn.
8. Coordination Compounds
 • Transition metals tend to form complex ions
• A complex ion has a central metal ion bound to one or more ligands
• A ligand is a Lewis base (electron donor) that bonds with metal
• A coordination compound is a neutral compound composed of a
complex ion combined with one or more counterions
• Alfred Werner in 1893 proposed primary valence (oxidation state on
central metal atom) and secondary valence (coordination number or
number of molecules or ions directly bound to the metal atom.)
• Coordinate covalent bonds (ligands) bond molecules to the central
metal ion
• Monodentate- ligands that donate only one electron pair to the central
metal
• Bidentate- ligands that can donate 2 pairs of electrons to the metal
(ox-oxalate and en)
• Polydentate- donate more than 2 pairs of electrons (EDTA)
• Chelate- a complex ion containing a bidentate of polydentate ligand
• Chelating Agent- coordinating ligand of a chelate
• Table 24.3 Common Geometries of Complex Ions

Coordination Shape Model Example

Number

2 Linear [Ag(NH3)2]+

4 (d8) Square Planar [PdCl4]2-

4 (d10) Tetrahedral [Zn(NH3)4]2+

6 Octahedral [Fe(H2O)6]3+

1. Bonding in Coordination Compounds

• Valence Bond Theory
○ A coordinate covalent bond is the overlap between a completely
filled atomic orbital and an empty atomic orbital. On a complex
ion, filled orbital is on ligand and empty orbital is on metal ion.
○ Metal ion orbitals are hybridized according to geometric
structure.

Geometry Hybridization

Linear Sp

Tetrahedral Sp3

Square Planar Dsp2

 Octahedral D2sp3

• Crystal Field Theory

○ Explains color and magnetism
○ CFT focuses on how electrons on ligands repel electrons in the
unhybridized metal d orbitals
○ D orbitals are split into higher and lower energy levels because
of arrangement of ligands

D orbitals in octahedral field

__ __

z2 x2-y2

__ __ __

xy yz xz

○ Difference in energy between the split d orbitals is the crystal

field splitting theory (Δ)
○ Δ is large in strong-field complexes that have low-spin
complexes
○ Δ is small in weak-field complexes that have high-spin
complexes
○ Ephoton= hv= hc/wavelength= Δ

The Color Wheel

 • Magnitude of Δ and whether strong-field or weak-field depends on
ligands attached to central metal ion

Large Δ -typically strong-field ligands Small Δ – typically

weak-field ligands

CN- > NO2- > en > NH3 > H2O > OH- >F- >
Cl- > Br- >I-

• As charge on metal ion increases, Δ increases, assuming same ligands

• Absorbing shorter wavelength, higher energy, higher Δ
• All Paired electrons- diamagnetic, Unpaired electrons- paramagnetic
• In octahedral complexes, only d4, d5, d6, and d7 metal ions can have low
and high-spin possibilities, d1, d2, and d3 will always have unpaired
electrons independent of Δ. In d8, d9, and d10 metal ions, 3 lower energy
orbitals are completely filled, so they must fill up the 2 higher orbitals
• Tetrahedral Orbitals- low 2 are x2-y2 and z2. High 3 are xy, yz, xz
• Square Planar Orbitals, Lowest 2 are xz, yz, then z2, then xy, then x2-y2.

Chapter 11- Liquids, Solids, and Intermolecular Forces

1. Condensed phases- liquids and solids- particles are close together and exert
moderate to strong attractive forces to each other
Phase Density Shape Volume IMF Strength

Liquid High Indefinite Definite Moderate

Solid High Definite Definite Strong

2. Crystalline solids have atoms or molecules that are arranged in a well-

ordered 3D array
3. Amorphous solids have atoms or molecules that have no long-range order
4. Solid---heat--- Liquid ---heat or reduce pressure  Gas
-----cool Cool or Increase Pressure
5. Strength of intermolecular forces determines phase of substance at a given
temperature
6. Intermolecular forces are generally much weaker than bonding forces.
Bonding forces are large charges acting at close distances while
intermolecular forces are small charges acting at longer distances.
7. Types of Intermolecular forces: dispersion forces, dipole-dipole forces,
hydrogen bonding, and ion-dipole force.
• Dispersion forces
○ Fritz W. London first recognized the nature of dispersion forces.
○ Dispersion forces are present in all molecules and atoms. They are
caused by fluctuations in the electron distribution within molecules or
atoms.
 ○ The uneven distribution of electrons at any instant is called an
instantaneous dipole or a temporary dipole.
○ If electrons are located more towards the left side of the atom, the
atom’s left side will be more negative and the right side will be more
positive.
○ The magnitude of dispersion forces depends on how easily the
electrons can move or polarize in response to an instantaneous dipole.
This ease depends on the # of electrons
○ A large electron cloud or molar mass has more dispersion force
○ Larger area for interaction increases strength of dispersion force
• Dipole-Dipole forces
○ Exist in all polar molecules, that have permanent dipoles that interact
with permanent dipoles of other molecules
○ Miscibility- the ability to mix without separating into two phases
(polar&polar, nonpolar& nonpolar)
• Hydrogen Bonding
○ A sort of super dipole-dipole force
○ Caused by a large electronegativity difference between hydrogen and
N,O, F that result in a fairly large partial positive charge in H and a
fairly large negative charge in N, O, F.
○ The small size of these molecules allow a close and strong attraction

• Ion-Dipole forces
○ Occurs when an ionic compound is mixed with a polar compound;
aqueous solutions of ionic compounds
○ For example, in NaCl, Cl- binds with the + end of H2O and Na+ binds to
the – end of H2O
○ Strongest type of intermolecular force

1. 11.4 Intermolecular Forces in Action: Surface Tension, Viscosity, and Capillary

Action
• Surface Tension
○ Molecules on the surface do not have as many neighbor
molecules to interact with compared to those under the liquid
○ The surface tension of a liquid is the energy required to increase
the surfice are by a unit amount.
○ Molecules on the surface of a liquid have higher potential energy
than those in the interior, liquids tend to minimize surface area
○ Surface tension increases with greater intermolecular forces and
decreases with smaller intermolecular forces
 • Viscosity
○ Defined as the resistanace of a liquid to flow
○ Measured in poises, 1g/cm.s
○ Viscosity is greater in substances with stronger intermolecular
forces
○ Increases in longer molecules
○ Depends on temperature because thermal energy partially
overcomes intermolecular forces; as temp rises, viscosity
decreases
• Capillary Action
○ The ability of a liquid to flow against gravity up a narrow tube
○ Results from the combination of cohesive and adhesive forces
○ Cohesive- attraction between molecules in a liquid
○ Adhesive- attraction between molecules and tube
○ Convex shape, Cohesive Forces>Adhesive Forces
○ Concave shape, Adhesive Forces>Cohesive Forces
1. Vaporization and Vapor Pressure
• The process by which thermal energy can overcome intermolecular
forces and produce a phase change from liquid to gas
• The higher the temperature, the greater the average energy of the
collection of molecules.
• Condensation-the opposite of vaporization- the phase transition from
gas to liquid
• Weaker IMF allow easier vaporization/evaporation
• Volatile- liquids that evaporate easily
• Nonvolatile- liquids that don’t evaporate easily
• The rate of vaporization increases with increasing temperature, surface
area
• Endothermic process, it takes energy to vaporize molecules in a liquid
• Condensation is exothermic; heat is released when gas condenses to a
liquid
• Heat of Vaporization is the amount of heat required to vaporize one
mole of a liquid to gas; always positive and depends on temperature
1. Vapor Pressure and Dynamic Equilibrium
• Dynamic equilibrium- the rate of condensation and rate of vaporization
are equal
• Vapor pressure- the pressure of a gas in dynamic equilibrium with its
liquid
• Weak IMF= high vapor pressure, Strong IMF= nonvolatile w/ low vapor
pressure
• When a system in dynamic equilibrium is disturbed, the system
responds so as to minimize the disturbance and return to a state of
equilibrium.- Le Chatelier’s principle.
 • As temperature increases, vapor pressure exponentially rises since
thermal energy increases.
• Boiling point- the temperature at which its vapor pressure equals the
external pressure.
• At the BP, all molecules including interior molecules have enough
energy to escape into gas phase
• Normal BP- the temperature at which its vapor pressure equals 1atm
• As long as liquid water is present, its temperature cannot rise above its
boiling point.
• Critical temperature- the temperature above which the liquid cannot
exist, regardless of pressure
• Critical pressire- the pressure required to bring about a transition to a
liquid at the critical pressure
• Supercritical fluid- when the liquid and gas phases both exist
simultaneously- have properties of both liquid and gases
11.Sublimation and Fusion p487
• Sublimation- the phase transition from solid to gas.
• Deposition- the phase transition from gas to solid
• Melting point (fusion)- molecules have enough thermal energy to
overcome IMF
• Melting/Fusion- the phase transition from solid to liquid
• Freezing- opposite of fusion- phase transition from liquid to solid
• After melting point is reaches, increase of temperature causes higher
rate of melting instead of raising temperature of solid
• Heat of fusion is positive/endothermic
• Freezing is exothermic, negative head of fusion
• In general, heat of fusion is less than heat of vap

12.Heating Curve for Water

• Segment 1- heating solid
• q=mass(g)Cs,ice (J/g.degC)ΔT
• Segment 2- Melting point phase change
• q= (number of moles)( ΔHfus)
• Segment 3- heating liquid
• q=(mass)(Cs, liq) ΔT
• Segment 4- Phase transition from liquid to gas
• q=(number of moles) ΔHvap
 • Segment 5- heating gas
• q=(mass)(Cs,steam) ΔT
13.Phase Diagrams

Regions-
Solid, Liquid, and Gas
Lines-
Fusion curve (melting/freezing)
Sublimation curve (sublimation/deposition)
Vaporization curve (vaporization/condensation)
Triple point- the point in the phase diagram that has unique set of
conditions at which 3 phases are equally stable and in equilibrium.
Critical Point- the point that represents the temperature and pressure
above which supercritical fluid exists

Crystalline Structures: Unit Cells and Basic Structures

Cubic Cell Atoms per Structure Coordination Edge Length Packing

Name Unit Cell Number in terms of r Efficiency
(fraction of
volume
occupied)

Simple Cubic 1 Cube with 6 2r 52%

 eighths

Body- 2 Simple Cubic 8 4r/ √3 68%

centered with one atom
Cubic in center

Face-centered 4 Cubic with 12 2 √2r 74%

Cubic atoms on
faces and
corners

1/8 at corners, ½ at faces

Chapter 12- Solutions

1.
• Solution- a homogeneous mixture of two or more substances
• Solvent- the majority component, Solute- the minority component
• Solution can be solid/liquid, liquid/gas, two liquids, or other combinations
• Aqueous solutions have water as solvent and solid, liquid, or gas as solute
• Solubility is the amount of the substance that will dissolve in a given
amount of solvent
• Solutions do not necessarily lower the potential energy of its constituent
particles.
• Entropy is a measure of energy randomization of energy dispersal in a
system.
• Relative Interactions and Solution Formation

Solvent-solute > Solvent-solvent Solution forms

interactions and solute-solute
interactions

Solvent-solute = Solvent-solvent Solution Forms

interactions and solute-solute
interactions

Solvent-solute < Solvent-solvent Solution may or

interactions and solute-solute may not form,
interactions depending on
relative disparity
 • “Like dissolves like”
• Common Polar Solvents- Water, Acetone(CH3COCH3)), Methanol(CH3OH),
Ethanol (CH3CH2OH)
• Common Nonpolar Solvents- Hexane(C6H14), Diethyl
ether(CH3CH2OCH2CH3), Toluene(C7H8), Carbon Tetrachloride(CCl4)
1. Energetics of Solution Formation
• ΔHsolute>0 Endothermic
• Hess’s law states: ΔHsoln= ΔHsolute(endothermic)+ ΔHsolvent(endothermic)+
ΔHmix(exothermic)
• ΔHsolvent(endothermic)+ ΔHmix(exothermic)= ΔHhydration(exothermic/negative)
• The heat of hydration is simply the enthalpy change that occurs when
1 mol of the gaseous solute ions are dissolved in water
• ΔHhydration is largely negative for ionic compounds
• Therefore, ΔHsoln= ΔHsolute(endothermic)+ ΔHhydration(exothermic/negative)
• ΔHsolute=- ΔHlattice
1. Solution Equilibrium and Factors Affecting Solubility
• The dissolution of a solute in a solvent is an equilibrium process like
phase change
• Dynamic equilibrium is reached when rates of dissolution and
deposition are equal
• Saturated solution- a solution in which the dissolved solute is in
dynamic equilibrium with the solid (or undissolved) solute. If you add
additional solute to a saturated solution, it will not dissolve.
• Unsaturated solution- a solution containing less than the equilibrium
amount of solute. If you add additional solute to an unsaturated
solution, it will dissolve.
• Supersaturated solution- a solution containing more than the
equilibrium amount of solute created under specific circumstances
• The solubility of most solids in water increases with increasing
temperature.
• Recrystallization- solid is put into water at an elevated temperature,
supersaturated and precipitates out of solution slowly, forming crystals
that reject impurities.
• The solubility of gases in liquids decreases with increasing temperature
• As pressure increases, gas is more soluble.
• Henry’s law: Sgas=kHPgas
• S is the solubility of the gas (M) kH is a constant of proportionality-
Henry’s law constant P is partial pressure of gas (atm)
1. Expressing Solution Concentration
• Dilute solution- contains small quantities of solute relative to the
amount of solvent
• Concentrated solution- contains large quantities of solute relative to
the amount of solvent
 Unit Definition Units

Molarity (M) Amount solute (mol) Mol

Volume solution (L) L

Molality (m) Amount solute (mol) Mol

Mass solvent (kg) kg

Mole Fraction (x) Amount solute (mol) None

Total amount of solute and solvent (mol)

Mole Percent (mol %) Amount solute (mol) x 100% None

Total amount of solute and solvent (mol)

Parts by mass Mass solute x multiplication factor

Mass solution

Percent by mass (%) Multiplication factor = 100 %

Parts per million by Multiplication factor= 106 ppm

mass (ppm)

Parts per billion by

mass (ppb) Multiplication factor= 109 ppb

Parts by volume (%, Volume solute x multiplication factor

ppm, ppb)
Volume solution

Table 12.5 Solution Concentration terms

2. Vapor pressure of solutions

 • The vapor pressure of a liquid is the pressure of the gas above the liquid
when the two are in dynamic equilibrium.
• The vapor pressure of the solution is lower than the vapor pressure of the
pure solvent
• Raoult’s law: Psolution= xsolventPosolvent
• Can be used to quantify the vapor pressure of a solution
• Psolution is the vapor pressure of the solution
• Psolvent is the vapor pressure of the pure solvent at the same temperature
• X is the mole fraction of solvent (h20 in aq sol)
• Ionic solutes- dissociate into component ions, e.g. a solution of NaCl has
Na+ and Cl-. .10mol of NaCl is .20 mol of dissolved particles
1. Ideal and Nonideal Solutions
• Ideal solution- a solution that follow’s Raoult’s law at all concentrations
for both the solute and the solvent
• Ideal solutions have solute-solvent interactions, solute-solute interactions,
and solvent-solvent interactions that are similar in magnitude.
• Ideal solutions- the solute dilutes solvent and behavior is ideal
• Two component using Raoult’s Law: PA=XAPoA, PB=XBPoB
• Ptotal= PA+PB

• Deviations from Raoult’s Law:

i. Solute-Solvent interactions(very strong) > solvent-solvent
interactions, solute prevents solvent from vaporizing,
ii.Solute-solvent interactions(very weak)< solvent-solvent
interactions, solute allows more vaporization that just with solvent.
iii.Both scenarios will be okay to work with Raoult’s law if dilute, but
effects will be significant if not dilute.
2. Freezing Point Depression, Boiling Point elevation, and Osmosis
• Nonvolatile solid solute will lower freezing pt (NaCl)
• Freezing point depression/Boiling point elevation
• Colligative properties- properties that depend on the amount of solute
and not the type of solute
• Freezing point Depression- ΔTf= m x Kf
• ΔTf is the change in temperature of the freezing point in Celcius degrees
relative to the pure solvent
• m is the molality of the solution
• Kf is the freezing point depression constant for the solvent=1.86 C/m for
water
• Boiling Point Elevation- ΔTb= m x Kb
• ΔTf is the change in temperature of the boiling point in Celcius degrees
relative to the pure solvent
• m is the molality of the solution
 • Kb is the boiling point depression constant for the solvent= 0.512 C/m for
water
• Osmosis- the slow of solvent from a solution of lower solute
concentration to one of higher solute concentration.
• Semipermeable membrane- a membrane that selectively allows some
substances to pass through but not others-separates two halves of a cell
• Osmotic pressure- The pressure required to stop the osmotic flow
• Osmotic pressure: Π = iMRT
• i is the van 't Hoff factor
• M is the molarity
• R=0.08206 L · atm · mol-1 · K-1 is the gas constant
• T is the thermodynamic (absolute) temperature (K)
• Colligative properties of Ionic Solutions
• Dissociation into two ions- van’t hoff factor(i) = moles of particles in
solution
Moles of formular units dissolved
• ΔTf= im x Kf
• ΔTb= im x Kb
• Colligative Properties and Medical Solutions
• Hyperosmotic- solutions that have osmotic pressures greater than those
of body fluids- take water out of cells/tissues
• Cells shrivel and loose water in hyperosmotic solutions
• Hyposmotic- solutions that pump wataer into cells- water enters cell in
these solutions and sometimes bursts
• Isosmotic (isotonic)- solutions that have equal osmotic pressures to those
of body fluids
1. Colloids
• Colloidal dispersion (colloid)- a mixture in which a dispersed substance is
finely divided in a dispersing medium. (Soapy water, Fog, Smoke,
Whipped Cream, milk.
• To define a colloid, one examines the size of the solute-like particles- if
particles are small (molecular sized), then it is a solution. If particles have
a diameter greater than one micrometer- it is a heterogeneous mixture
• IF particles are between 1nm to 1000nm, mixture is colloid
• Brownian motion- random jittery motion exhibited by colloidal particales-
caused by collisions with molecules in liquid. Brownian motion helped
confirm the molecular and atomic nature of matter
• Soap has an ionic Na+ head but a long nonpolar tail- forms micelles-
nonpolar tails are oriented inward and ionic heads are outwards to
interact with water via ion-dipole forces.
• Tyndall effect- the scattering of light by a colloidal dispersion
• Colloids can be dispersed macromolecules or clusters of molecules; blood
is a colloid; hemoglobin is large and scatters light.
• Colloids are kept stable by electrostatic repulsions on surfaces- micelles
repel other micelles- heating can destroy- makes stronger collisions to
break electrostatic repulsion. Adding electrolytes to colloids can also
disrupt electrostatic repulsions and destroy the colloid.