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Chemistry

05/14/2015

All atoms want to be a noble gas. A filled outer shell


Atoms gain electrons so that anion has a noble-gas outer electron
configuration
Atoms lose electrons so that cation has a noble-gas outer electron
configuration

What is the charge of a monatomic ion of nitrogen, the nitride ion?


-3
Which element forms a stable 2+ cation?
Ba
Isoelectronic: have the same number of electrons, and hence the same
ground-state electron configuration.
Na+: [Ne]
Al3+: [Ne]
F+: 1s22s22p6 or [Ne]
What neutral atom is isoelectronic with H-?
Helium
When a cation is formed from an atom of a transition metal, electrons are
always removed first from the ns orbital and then form the (n-1)d orbitals.
Fe: [Ar]4s23d5
Fe2+: [Ar]4s03d5
Fe3+: [Ar]4s03d5 or [Ar]3d5
If you gain electrons, add one in normal order.
Ife you lose electron, take them from the highest energy level.

If you have a fully filled orbital youll have extra energy


Cobalt: [Ar]4s23d7
Cobalt (IV): [Ar]3d5
Review Questions
Which is not an allowable set of quantum numbers?
N=2, l=2, ml=-2, ms=+1/2
Which quantum numbers could be expressing an electron in this
orbital?
F orbital, l must be equal to 3.
N=4, l=3, ml=+2, ms=-1/2
Give the electron configuration for Br 1s22s22p63s22p64s23d104p6
Give the electron configuration for Mn
1s22s22p63s23p64s23d5
Give the electron configuration for Fe3+
1s22s22p63s23p63d5

Give the valence electrons of F


7
Give the valence electrons of iodine.
7
Give the valence electrons of Sr.

2
What is the minimum energy needed to eject an electron if it is ejected
by a green light photon at 500nm? (have to convert nm to m; multiple by
10=-9)
3.98 x 10-19 J
o c = v
o = hv
o h = 6.626 x 10-34 Js
o c = 3.00 x 108 m/s
A wavelength of 0.325 pm ejects an electron with an energy of 3.035 x
-19
10 J. What is the binding energy for the electron in Joules?
1 pm = 1x10-12 m
Total E = binding E +E of ejected e hc/ = binding E + 3.035 x 10-19 J
6.12 x 10-13 J = binding E

Magnetism
Paramagnetic it has unpaired electrons.
Diamagnetic has all electrons paired.
o Noble gases are not affected by magnetism.
Effective nuclear charge (Zelf) is the positive charge felt by an electron
Zelf =Z ; 0 < < Z ( = shielding constant)
Zelf Z number of inner or core electrons

This increases as you go to the right and down. This has an inverse
reaction to the radius.
Atomic Radii
Metallic radius: two atoms just next to each other. Not a lot of
orbital overlap. Nonbonding Radius.
Covalent Radius: Bonding Radius.
Which element would have the smallest radius? The one in the top
right.
If you add more electrons (ions) the Zelf is going to decrease and
the radius increases. Cations are drawn nearer to the nucleus and
anions are less attractive to the nucleus.
o Cations are always smaller than atom from which it is formed
o Anions are always larger than atom from which it is formed

Ionization energy is the minimum energy (kJ/mol) required to remove


an electron from a gaseous atom in its ground state.
I1 + X (g) --> X+(g) + e- I1 first ionization energy
I1 < I2 < I3
Noble gases have the highest ionization energy
Lowest in ionization when they have a single electron
Upward to the right it gets higher.
Which of the following elements has the smallest first ionization
energy? K

Electron Affinity: the negative of the energy change that occurs when
an electron is accepted by an atom in the gaseous state tot form an anion.
X (g) + e- X- (g)
F (g) + e- X- (g) H = -328 kJ/mol
EA = +328 kJ/mol
The Halogens have the highest electron affinity

Metals versus Nonmetals


Metals
o Metals have a luster or shine
o Metals are good conductors of heat/electricity
o Most metals are solid at room temperatures (all except
mercury)
o Metals are malleable, or can be shaped or bent and the metal
will not break
o Most metals will react with acids
Nonmetals
o Nonmetals do not have a luster, they are dull in appearance
o Nonmetals are poor conductors of heat and electricity
o Nonmetals can be solid, liquid, or gas at room temperature
o Nonmetals are not malleable; when pressure is placed on
them, the nonmetals will break
o Most nonmetals will not react with acids
Metallic character increases towards the bottom left

Alkali Metals: Group 1A Elements (ns1, n 2); stored away from air
Red-Ox
Reacts with water to form hydroxide bases
o 2Na(s) + 2H2)(l) 2NaOH(aq) + H2(g)
Oxidation to form metal oxides

o 4Na(s) + O2(g) 2Na2O(g)


Oxidation to form metal halides
o 2Na(s) + Cl2(g) 2NaCl
Lithium
Sodium
Potassium
Rubidium
Cesium
Alkaline Earth Metals: Group 2A Elements (ns2, n 2)
High 1st and 2nd Ionization Energies
o M M+2 + 2e Reacts with water to form hydroxide bases
Group 3A Elements (ns2np1, n 2)
Oxidation to form metal oxides
Hydrogen Single displacement reactivity
Icosagens/ Triels: Group 3A Elements (ns2np1, n 2)
Oxidation to form metal oxides
Hydrogen-single displacement reactivity
Group 4A Elements (ns2np2, n 2)
Tetragens/Tetrals
Hydrogen-single displacement reactivity
Pnictogens: Group 5A Elements (ns2np3, n 2)
Oxides react with water to produce acids
Chalcogens: Group 6A Elements (ns2np4, n 2)
Oxides react with water to produce acids in this case: sulfuric
acid, a component of acid rain.
Halogens: Group 7A Elements (ns2np5, n 2)
High electron affinity
Binary acids form when halogens are reached with hydrogen gas
Electronegativity: affinity for electrons
Trend increases to the top right
Noble Gases: Group 8A Elements (ns2np6, n 2)
Completely filled ns and np subshells
Highest ionization energy

Valence electrons: the outer shell electrons of an atom. The valence


electrons are the electrons that participate in chemical bonding.
Explains how atoms bond together to make molecules

Lewis electron-dot structures


o Dots = electrons
o Predictive power
Types of Bonds
Elements will gain, lose, or share electrons to attain the electron
configuration of the noble gas closest to them in the periodic table.
o Ionic
Metal + Non-metal
Electron are transferred
o Covalent
Non-metal + Non-metal
o Metallic
Metal + Metal
Octet Rule (8 valence electrons)
Eight valence electrons are particularly stable
Filled outer electron (valence electron) shell
Exception is He cause with 2 electrons it is filled.
Ions Relating Group Number to Ionic Charge.
Sum of the charges in an ionic compound must be zero overall.
Identify which element is the cation and which is the anion
Lattice energy: the energy required to completely separate one mole
of a solid ionic compound into gaseous ions.

Coulombs Law: E=k(Q+Q-)/r

Polar covalent bond or polar bond: a covalent bond with greater


electron density around one of the two atoms; unequal sharing
Electronegativity: the ability of an atom to attract toward itself the
electrons in a chemical bond
Electron Affinity is measureable, Cl is highest
Electronegativity is relative, F is highest

Classification of bonds by difference in electronegativity


0.4; Covalent
0.4< and <2; Polar Covalent
o Only the CH bond is considered nonpolar covalent
2 Ionic
Molecular orbital theory
Bonds are formed from interaction of atomic orbitals to form
molecular orbitals.
Antibonding molecular orbitals have higher energy and lower
stability than the atomic orbitals from which it was formed
Bonding molecular orbitals have lower energy and greater stability
than the atomic orbitals from which it was formed

Bond order = (number of electrons in bonding MOs-number of


electrons in antibonding MOs)
Molecular orbital (MO) Configurations
The number of molecular orbitals formed is always equal to the
numner of atomic orbitas combined
The more stable the bonding MO, the less stable the corresponding
antibonding MO
The filling of MOs proceeds from low to high energies
Each MO can accommodate up to two electrons
Oxygen tends to be paramagnetic
Energy cannot be created or destroyed.
It only changes form, we dont get extra or lose it.
Energy: the capacity to do work
Kinetic Energy: Due to motion
o Thermal Energy: Associated with Temperature
Potential Energy: Due to position or composition
o Chemical Energy: Associated with Positions of Electrons and
Nuclei
Thermodynamics
Thermodynamics is the study of energy and its interconversions
The First Law of Thermodynamics is the Law of Conservation of
Energy
This means that the total amount of energy in the universe is
constant
You can therefore never design a system that will continue to
produce energy without some source of energy
Units of Energy
Joule (J) is the amount of energy needed to move a 1-kg mass a
distance of 1 meter
o 1 J = 1 N*m = 1 kg*m2/s2

calorie (cal) us the amount of energy needed to raise the


temperature of one gram of water 1C
o kcal = energy needed to raise 1000g of water 1C
o food Calories = kcals
Energy Diagrams
Energy diagrams are a graphical way og showing the direction of
energy flow during a process
If the final condition has a larger amount of internal energy than
the initial condition, the change in the internal energy will be +
If the final condition has a smaller amount of internal energy than
the initial condition, the change in the internal energy will be
Energy Flow
When energy flows out of a system, it must all flow into the
surrounding
When energy flows out of a system, Esystem is
When energy flows into the surroundings, E surroudings is +
Therefore: Esystem = Esurroudings
Exothermic process is any process that gives off heat - transfers
thermal energy from the system to the surroundings
Endothermic process is any process in which heat has to be supplied
to the system from the surroundings
Electrostatic (Lattice) Energy
Lattice energies become more exothermic (more negative) with
increasing charge
Lattice energies become less exothermic (less negative) with
increasing radii
Need to learn Born-Haber Cycle
Enthalpy change required to break a particular bond in one mole of
gaseous molecules is the bond enthalpy or bond energy
Bond enthalpies: Single bond< Double bond< Triple bond
Imagine reaction proceeding by breaking all bonds in the reactants
and then using the gaeous atoms to form all the bonds in the products

H0 = total energy input total energy released


= BE(reactants) BE(products)
Standard Conidionts
Standard state is the state of a material at a defined set of
conditions
o Pure gas at exactly 1 atm pressure
o Pure sokid or liquid in its most stable form at exactly 1 atm
oressure and temperature of interest
Usually 25oC
o Substance in a solution with concentration 1 M
The standard enthalpy change, Ho, is the enthalpy change when
all reactant and products are in their standard states
The standard enthalpy of formation, Hfo, is the enthalpy change for
the reaction forming 1 mole of a pure compound from its
constituent elements
o The elements must be in their standard states
o The Hfo for a pure element in its standard state = 0 kJ/mol
By definition
Formation reactions
Reactions of elements in their standard state to form 1 mole of a
pure compound
o
If you are not sure what the standard state of an element is,
find the one in Appendix IIB that has a Hfo
o

Calculating Standard Enthalpy


Any reaction can be written as the sum of formation reactions (or
the reverse of formation reactions ( for the reactants and products
The Ho for the reaction is then the sum of the Hfo for the
component reactions
When reaction is multiplied by a factor, Hrxn is multiplied by that
factor

o Because Hrxn is extensive


If a reaction is reversed, then the sign of H is changed
If a reaction can be expressed as a series of steps, then the Hrxn
for the overall reaction is the sum of the heats of reaction for each
step

Gases
Elements that exist as gases at 25oC and 1 atm
o Hydrogen
o Nitrogen
o Nobles
Physical Characteristics of Gases
Gases assume the volume and shape of their containers
Gases are the most compressible state of matter
Gases will mix evenly and completely when confined to the same
container
Gases have much lower densities than liquids and solids.
Boyles law: P a 1/V (at constant n and T)
Charles law: V a T (at constant n and P)

Avogadros Law: V a n (at constant P and T)


PV = nRT
T is in Kelvin K = C +273
STP: Standard temperature and pressure
1 mole of gas, at 1 atm, 273oK, 22.414L

M = dRT/P
Kinetic Molecular Theory of Gases
A gas is composed of molecules that are separated from each other
by distances far greater than their own dimensions. The molecules
can be considered to be points, that is, they possess mass but have
negligible volume.
Gas molecules are in constant motion in random directions and they
frequently collide with one another. Collisions among molecules are
perfectly elastic.
Gas molecules exert neither attractive nor repulsive forces on one
another
The average kinetic energy of the molecules is proportional to the
temperature of the gas in kelvins. Any two gases at the same
temperature will have the same average kinetic energy.
o KE = m2 = 3/2 nRT
The lighter you are the faster you are flying.
Gas diffusion: the gradual mixing of molecules of one gas with
molecules of another by virtue of their kinetic properties
R1/r2 = sqrt(M2/M1)
Gas effusion: the process by which gas under pressure escapes from
one compartment of a container to another by passing through a small
opening.
Deviations from ideal behavior 1 mole of ideal gas. As the pressure
increases you see a deviation from the ideal gas

Van der Waals equation for non-ideal gases


(P + an2/V2)(V nb) = nRT
The force that we would expect it to have is less if there are other
molecules in the same proximity.
Oxygen Toxicity
Elevated Partial Pressure
Intermolecular Forces for Liquids and Solids
Phase is a homogenous part of the system in contact with other
parts of the system but separated from them by a well defined
boundary
Intermolecular forces are attractive forces between molecules
Intramolecular forces hold atoms together in a molecule
o Intermolecular versus intramolecular
41kJ to vaporize 1 mole of water (inter)
930kJ to break all O-H bonds in 1 mole of water (intra)
Intermolecular forces are the attractive forces that exist between
molecules
In order of increasing strength, these are
o London dispersion forces
o Dipole-dipole interactions

o Hydrogen bonding
o Ion-dipole forces
The strength of the intermolecular forces determines the physical
properties at a given temperature.
Intermolecular Forces
London Dispersion Forces
Very weak interactions due to the momentary changes in electron
density in a molecule
The change in electron density creates a temporary dipole
All covalent compounds exhibit London dispersion forces
The larger the molecule, the larger the attractive force, and the
stronger the intermolecular forces
The more polarizable the molecule, the greater the London
dispersion forces
Polarizability is the ease with which the electron distribution in the
atom or molecule can be distorted
Increase with:
o Greater number of electrons
o More diffuse electron cloud
Attractive forces between polar molecules
Positive to negative
Dipole-dipole interactions are the attractive forces between the
permanent dipoles of two polar molecules

The boiling point is the temperature at which liquid is converted to gas.


Both propane and butane have London dispersion forces and nonpolar
bonds
In this case, the larger molecule will have a larger surface area and
stronger attractive forces
A general rule for solubility is that like dissolves like in terms of
comparable polarities
Polar and ionic solids are usually soluble in polar solvents
Nonpolar solids are usually soluble in nonpolar solvents
Polar liquids are usually miscible
Nonpolar liquids are usually miscible
Polar and nonpolar liquids are usually not miscible for most extents.
Condensation is exothermic.
The stronger the intermolecular forces, the lower the vapor pressure at
a given temperature and the slower it evaporates
Smaller surface area: slower evaporation
Larger surface area: faster evaporation
Viscosity
Viscosity is a measure of a fluids resistance to flow freely

A Viscous liquid feels thick


Compounds with strong intermolecular forces tend to be more
viscous than compounds with weaker forces
Substances composed of large molecules tend to be more viscous,
too, because large molecules do not slide past each other as freely
Surface Tension
A measure of the resistance of a liquid to spread out
Interior molecules in a liquid are surrounded by intermolecular
forces on all sides
Surface molecules only experience intermolecular forces from the
sides and from below
The stronger the intermolecular forces, the stronger the surface
molecules are pulled down toward the interior of a liquid and the higher the
surface tension.
Water has a very high surface tension because of its strong
intermolecular hydrogen bonding
Small objects can seem to float on the surface of water
These normally heavy objects appear to float
It ends at the critical point where the liquid and vapor are no longer
distinguishable
Sublimation
The heat added to the system at the melting and boiling points goes
into pulling the molecules farther apart from each other
The temperature of the substance does not rise during the phase
change
Q = n H
Rate of Evaporation
Relationship of vapor pressure to change in temperature
Clausius-Clapeyron Equation
Ln (P2/P1) = ((Hvap)/(R)) * ((1/T2)-(1/T1))
Solids
o Amorphous-no particular order in the arrangement of
particles
Three types of interactions in the solution process:
Solvent-solvent interaction
Solute-solute interaction
Solvent-solute interaction
Heat of hydration

When solvation releases more energy than that required to


separate particles, the overall process is exothermic
o Heat is released
o Hot packs
When the separation of particles requires more energy than is
released during solvation, the process is endothermic
o Heat is absorbed
o Cold packs

A saturated solution contains the maximum amount of a solute that


will dissolve in a given solvent at a specific temperature
An unsaturated solution contains less solute than the solvent has the
capacity to dissolve at a specific temperature
A supersaturated solution contains more solute than is present in a
saturated solution at a specific temperature
Sodium acetate crystals rapidly form when a seed crystal is added a
supersaturated solution of sodium acetate.
For most ionic and molecular solids, solubility in a liquid generally
increases as temperature increases
By dissolving a solid in a solvent at high temperature and allowing it
to colll slowly, a supersaturated solution can be made
A supersaturated solution contains more than the predicted
maximum amount of solute at a given temperature
Fractional crystallization: the separation of a mixture of something
Solubility of gases decrease as you increase temperature
The solubility of a gas in a liquid is proporiotnal to the pressure of the
has over the solution (Henrys Law) S=kP
S is the concentration
K is the constant
P is the pressure

Pa = (naRT)/V
Pb = (nbRT)/V
Pt = Pa + Pb
Molarity M = moles of solute/ liters of solution
Molality m = moles of solute/ mass of solvent (kg)
Colligative properties: depend only on the number of solute particles in
solution and not on the nature of the solute particles.
Van Hoff Factor
Boiling Point Elevation Tb = iKbm
Freezing Point Depression Tf = iKfm
Osmotic Pressure () = iMRT