Concept Summary 1

Subatomic Particles
Proton, positive charge; neutron, no charge; electron, negative charge
The nucleus contains the protons and neutrons, while the electrons reside in
regions of space around the nucleus
Atomic number is the number of protons in a given element
Mass number is the sum of an element's protons and neutrons
Atomic Weights and Isotopes
Isotopes are atoms of a given element (same atomic number) that have different
numbers of neutrons in their nuclei (different mass number)
o Atomic masses listed in the periodic table are averages of the various
isotopes of an element weighted according to their relative abundance
o Most isotopes of elements are identified by the element followed by the
mass number (e.g., carbon-12, carbon-13, carbon-14)
o The three isotopes of hydrogen go by different names: protium, deuterium,
and tritium
Bohr's Model of the Hydrogen Atom
The Bohr model of the atom consists of a dense, positively charged nucleus
surrounded by electrons revolving around the nucleus in defined pathways of
distinct energy levels calledorbits
o The energy difference between energy levels is called a quantum
o The energy of an electron is quantized, which means that there is not an
infinite range of energy levels available to an electron; electrons can exist
only at certain energy levels, and the energy of an electron increases the
farther it is from the nucleus
The atomic absorption spectrum of an element is unique; for an electron to jump
from a lower energy level to a higher one, it must absorb an amount of energy
precisely equal to the energy difference between the two levels
When electrons return from the excited state to the ground state, they emit an
amount of energy that is exactly equal to the energy difference between the two
levels; every element has a characteristic atomic emission spectrum, and
sometimes the electromagnetic energy emitted corresponds to a frequency in the
visible light range
Quantum Mechanical Model of Atoms
The quantum mechanical model posits that electrons do not travel in defined orbits
but rather in complex patterns called orbitals; an orbital is a region of space around
the nucleus defined by the probabilities of finding an electron in that region of
space
The Heisenberg uncertainty principle states that it is impossible to know both an
electron's position and its momentum at the same time
There are four quantum numbers; these numbers completely describe any
electron in an atom
o The principal quantum number, n, describes the average energy of an
orbital
o The azimuthal quantum number, l, describes the subshells within a given
principal energy level
o The magnetic quantum number, m
l
, specifies the particular orbital within
a subshell where an electron is likely to be found at a given moment in
time
o The spin quantum number, m
s
, indicates the spin orientation of an
electron in an orbital
Designating the location of electrons using the principal energy levels, subshells,
and orbitals is the electron configuration
o For example, 1s
2
2s
2
2p
6
3s
2
is the electron configuration for magnesium: a
neutral magnesium atom has 12 electrons two in the s-orbital of the first
energy level, two in the s-orbital of the second energy level, 6 in the p-
orbitals of the second energy level, and 2 in the s-orbital of the third energy
level; the two electrons in the s-orbital of the third energy level are the
valence electrons for the magnesium atom
Electrons fill the principle energy levels and subshells according to increasing
energy, which can be determined by the (n + l) rule; electrons fill orbitals according
to Hund's rule, which states that electrons prefer to be unpaired, with parallel spins
Valence electrons are those electrons in the outermost shell and/or those available
for interaction (bonding) with other atoms
o For the representative elements, the valence electrons are found in s-
and/or p-orbitals
o For the transition elements, the valence electrons are found in s-, d-, and f-
orbitals
o Many atoms interact with other atoms to form bonds that complete the
octet in the valence shell
Concept Summary 2
The Periodic Table
The periodic table of the elements organizes the elements according to their
atomic numbers and reveals a repeating pattern of similar chemical and physical
properties
o Elements in the same row are in a period and have the same principal
energy level, n
o Elements in the same column are in a group and have the same valence
shell electron configuration
Periodic Properties of the Elements
Effective nuclear charge (Z
eff
) is the net positive charge experienced by electrons
in the valence shell and forms the foundation for all periodic trends
o Z
eff
increases from left to right across a period, with little change in value
from top to bottom in a group
o Valence electrons become increasingly separated from the nucleus as the
principal energy level, n, increases from top to bottom in a group
Atomic radius decreases from left to right across a period and increases from top
to bottom in a group
Ionization energy (IE) is the amount of energy necessary to remove an electron
from the valence shell; it increases from left to right across a period and decreases
from top to bottom in a group
Electron affinity is the amount of energy released when an atom gains an
electron in its valence shell; it increases from left to right across a period and
decreases from top to bottom in a group
Electronegativity is a measure of the attractive force that an atom in a chemical
bond will exert on the electron pair of the bond; it increases from left to right across
a period and decreases from top to bottom in a group
Types of Elements
The elements on the periodic table belong to one of 3
classes: metals, nonmetals, andmetalloids; each has a characteristic feature and
location on the periodic table
o Metals: shiny, conduct electricity well, malleable, ductile, found on left side
and middle of the periodic table
o Nonmetals: dull, poor conductors of electricity, brittle, found on right side
of the periodic table
o Metalloids: possess characteristics of both metals and nonmetals, found
in a stairstep fashion, starting with boron, separating metals from
nonmetals
The Chemistry of Groups
Alkali metals typically take on an oxidation state of +1 and prefer to lose an
electron to achieve noble gas configuration; they and the alkaline earth metals are
the most reactive of all metals
Alkaline earth metals take on an oxidation state of +2 and can lose two electrons
to achieve noble gas configuration; they and the alkali metals are the most reactive
of all metals
Halogens have an oxidation state of 1 and prefer to gain an electron to achieve
noble gas configuration; these nonmetals have the highest electronegativities
Noble gases have a stable octet in their valence shell in their standard state and
prefer not to give up or take on additional electrons; they have very high ionization
energies and virtually nonexistent electronegativities
Transition metals are unique metals because they take on multiple oxidation
states, which explains their ability to form colorful complexes with nonmetals in
solution
Concept Summary 3
Bonding
Chemical bonds can be ionic or covalent
Ionic Bonds
An ionic bond is formed from the transfer of one or more electrons from an
element with a relatively low electronegativity to an element with a relatively high
electronegativity
o The resulting electrostatic attraction between the ions causes them to
remain in proximity, forming the bond
Ionic compounds have unique physical and chemical properties
o Ionic compounds tend to dissociate in water and polar solvents
o Ionic solids tend to have high melting points
Covalent Bonds
A covalent bond is formed from the sharing of electrons between two elements of
similar electronegativities
Covalent bonds can be categorized as nonpolar, polar, or coordinate covalent,
based on the nature of the elements
o Nonpolar bonds result in molecules in which both atoms have exactly the
same electronegativity; some bonds are considered nonpolar when there
is a very small difference in electronegativity between the atoms, even
though they are technically slightly polar
o Polar bonds form when there is a signifi cant difference in
electronegativities but not enough to transfer electrons and form an ionic
bond
o Coordinate covalent bonds result from a single atom providing both
electrons in an electron pair while the other atom does not contribute;
coordinate covalent bonds are most often found in Lewis acid/base
chemistry
Lewis dot symbols are a chemical representation of an atom s valence electrons
Drawing a complete Lewis dot structure requires a balance of valence, bonding,
and nonbonding electrons in a molecule or ion
Formal charge is calculated using the formal charge equation included in the
equation list for this chapter, with an end goal of minimizing the charge on all
atoms in the molecule or ion
For any molecule with a pi system of electrons, resonance structures exist; these
represent all of the possible confi gurations of electrons stable and unstable
that contribute to the overall structure
Recognize that there are many exceptions to the octet rule, as some atoms do not
need a full octet while others may exceed the octet in their valence shells
The valence shell electron pair repulsion (VSEPR) theorypredicts the three-
dimensional molecular geometry of covalently bonded molecules
The polarity of moleculesis dependent on the dipole moment of each bond and
the sum of the dipole moments in a molecular structure
o All polar molecules contain polar bonds, but nonpolar molecules may
contain polar and/or nonpolar bonds
Sigma and pi bonds describe the patterns of overlap observed when molecular
bonds are formed; sigma bonds are the result of a head-to-head overlap, and pi
bonds are the result of two parallel electron cloud densities
The Intermolecular Forces
Intermolecular forcesare electrostatic attractions between molecules; they
include the following:
o London forcesare the weakest interactions but are present in all atoms
and molecules; as the size of the atom or structure increases, so does the
corresponding dispersion force
o Dipole-dipole interactions, which occur between the oppositely charged
ends of polar molecules, are stronger than London forces; these
interactions are evident in the solid and liquid phases and negligible in the
gas phase due to the distance between particles
o Hydrogen bonds are a specialized subset of dipole-dipole interactions
involved in intra- and intermolecular attraction; hydrogen bonding occurs
when hydrogen is bonded to one of three atoms fl uorine, oxygen, or
nitrogen and is approximately one tenth the strength of covalent bonding



Concept Summary 7
The Gas Phase
Gases are the least dense phase of matter
Gases, like liquids, are fluids
o Fluids respond to shearing forces
o Fluids conform to the shape of their containers
Gases, unlike liquids, are compressible
The state of a gas system can be characterized by:
o Temperature
o Pressure
o Volume
o Number of moles
Ideal Gases
Standard temperature and pressure (STP) is 1 atm and 273 K
Assumes negligible mass and volume of gas molecules
Kinetic Molecular Theory of Gases
Assumes gas molecules have no:
o Volume
o Intermolecular forces
Proposes that gas molecules are:
o In constant random motion
o Colliding in perfectly elastic collisions with each other and the walls of the
container
o Moving with an average kinetic energy proportional to their temperatures
Graham's law describes the behavior of diffusing or effusing mixtures of gases;
the gas with the lower molecular weight will diffuse or effuse faster
Ideal Gas Behavior
Regardless of the identity of the gas, equimolar amounts of two gases will occupy
the same volume at the same temperature and pressure
1 mole of an ideal gas occupies 22.4 L at STP
The ideal gas lawPV = nRT describes the relationship between the four variables
of the gas state for an ideal gas
Boyle's lawis a special case of the ideal gas law for which temperature is held
constant; it shows an inverse relationship between pressure and volume
Charles' lawis a special case of the ideal gas law for which pressure is held
constant; it shows a direct relationship between temperature and volume
Dalton's law of partial pressures states that individual gas components of a
mixture of gases will exert individual pressures in proportion to their mole fractions
o The total pressure of a mixture of gases is equal to the sum of the partial
pressures of the component gases
Real Gases
Real gases deviate from ideal behavior under high pressure and low temperature
conditions
The van der Waals equation of state is used to correct for intermolecular
attractions and molecular volume



















Concept Summary 4
Compounds
Compounds are pure substances composed of two or more elements in a fixed
proportion
They can react to form new compounds and be broken down by chemical means
into their elements
Molecules and Moles
Molecular weight is the mass in amu of the constituent atoms in a compound as
indicated by the molecular formula
Molar mass is the mass of one mole (Avogadro's number or
6.022 10
23
molecules) of a compound; usually measured in g/mol
Equivalents are moles of the species of interest; equivalents are most often seen
in the following reactions:
o Acid/base chemistry as moles of hydronium or hydroxide ions
o Redox reactions as moles of electrons
Gram equivalent weight is a measure of the mass of a substance that can donate
one equivalent of the species of interest
Normality is the ratio of equivalents per liter; it is related to molarity by the number
of equivalents present per molecule of compound
Representation of Compounds
The law of constant composition states that any pure sample of a compound will
contain the same elements in the same mass ratio
The empirical formula is the smallest whole number ratio of the elements in a
compound
The molecular formula is either the same as or a multiple of the empirical
formula; it gives the exact number of atoms of each element in a compound
To calculate percent composition by mass, determine the mass of the individual
element and divide by the molecular weight of the compound
Types of Chemical Reactions
Combination reactions occur when two or more reactants combine to form one
product
Decomposition reactions occur when one reactant is chemically broken down
into two or more products
o Decomposition is often accomplished with heat or electrolysis
Displacement reactions occur with when one or more atoms or ions of one
compound are replaced with one or more atoms or ions of another compound.
o Single displacement reactions occur when an atom or ion of one
compound is replaced with an atom or ion of another element
o Double displacement reactions occur when elements from two different
compounds trade places with each other to form two new compounds;
double displacement reactions include:
Neutralization reactions in which an acid reacts with a base to
form a salt and water
Net ionic equations ignore spectator ions to focus only on the
species that actually participate in the reaction
Balancing Chemical Equations
Balanced equations are determined using the following steps in order:
o Balancing the non-hydrogen and non-oxygen atoms
o Balancing the oxygen atoms, if present
o Balancing the hydrogen atoms, if present
o Balancing charge when necessary
Applications of Stoichiometry
Balanced equations can be used to determine:
o The limiting reactant , which is the reactant that will be consumed first in
a chemical reaction
Theoretical yield is the yield if all of the limiting reactant is consumed with no side
reactions
o Actual yield is typically lower than theoretical yield
Percent yield is calculated by dividing actual yield by theoretical yield
Equations to Remember






Concept Summary 5
Chemical Kinetics
Chemical kinetics proposes a series of steps that make up the overall reaction
The slowest step, also known as the rate-determining step , limits the maximum
rate at which the reaction can proceed
Reaction Rates
Reaction rates are measured in terms of the rate of disappearance or appearance
of a reactant or product
Rate laws take the form of rate = k[A]
x
[B]
y

Rate laws must be determined from experimental data
Reactions occur when molecules collide with:
o Proper orientation
o Kinetic energy equal to or greater than the energy of the transition state;
this is known as the activation energy
Reaction Rates can be increased by:
o Increasing the concentration of reactant (except for zero order reactions)
o Increasing the temperature
o Changing the medium
o Adding a catalyst
Equilibrium
Reversible reactions eventually reach a state in which:
o Energy is minimized
o Entropy is maximized
o The concentration of reactants and products remains equal because the
rate of the forward reaction equals the rate of the reverse reaction
The law of mass action gives the equilibrium constant K
eq

o K
eq
is the ratio of products to reactants at equilibrium for a reaction at a
constant temperature
o K
eq
is a constant
o Pure solids and pure liquids are not included in calculating K
eq

The reaction quotient Q
c
is a calculated value involving reactant and product
concentrations at any time within a reaction
Comparison of Q
c
to K
eq
will tell you where the reaction is with respect to its
equilibrium state
o Q
c
< K
eq
, G < 0, reaction proceeds in forward direction
o Q
c
= K
eq
, G = 0, reaction is in dynamic equilibrium
o Q
c
> K
eq
, G > 0, reaction proceeds in reverse direction
Le Ch telier's Principle
When a chemical system experiences a stress, it will react to restore equilibrium
Stresses applied may be:
o Concentration changes
Increasing the concentration of reactants or decreasing the
concentration of products will shift the reaction to the right
Decreasing the concentration of reactants or increasing the
concentration of products will shift the reaction to the left
o Pressure changes with changes in volume
Increasing the pressure on a gaseous system will shift the reaction
towards the side with fewer moles of gas
Decreasing the pressure on a gaseous system will shift the
reaction towards the side with more moles of gas
Changing the pressure of a system without changing the partial
pressures of the reactants and products will have no effect on the
system
o Temperature changes
Increasing the temperature of an endothermic reaction or
decreasing the temperature of an exothermic reaction will shift the
reaction towards the products
Decreasing the temperature of an endothermic reaction or
increasing the temperature of an exothermic reaction will shift the
reaction towards the reactants
Equations to Remember













Concept Summary 6
Systems and Processes
Systems are characterized based on what is exchanged with the surroundings
o Isolated systems exchange neither matter nor energy
o Closed systems can exchange energy but not matter
o Open systems can exchange energy and matter
Processes can also be characterized based on a single constant property
o Isothermal processes occur at a constant temperature
o Isobaric processes occur at a constant pressure
o Adiabatic processes exchange no heat with the environment
States and State Functions
State functions describe the physical properties of an equilibrium state; they are
pathway independent and include:
o Temperature
o Volume
o Density
o Enthalpy
o Entropy
o Pressure
o Internal energy
o Gibbs free energy
Standard conditions are 298 K and 1 atm, and the standard state of an element
is the most prevalent one under standard conditions; standard enthalpy,
standard entropy, andstandard free energy are all calculated under standard
conditions
Heat
Temperature and heat are not the same thing
o Temperature is a scaled measure of the average kinetic energy of a
substance
o Heat is the transfer of energy that results from differences of temperature
between two substances
Enthalpy
Enthalpy is a measure of the potential energy of a system found in intermolecular
attractions and chemical bonds
Hess's law states that the total change in potential energy of a system is equal to
the changes of potential energies of the individual steps of the process
Enthalpy can also be calculated using heats of formation, heats of combustion, or
bond dissociation energies
Entropy
Entropy, while often thought of as disorder, is a measure of the degree to which
energy has been spread throughout a system or between a system and its
surroundings
o Entropy is a ratio of heat transferred per mole per unit Kelvin
o Entropy is maximized at equilibrium
Gibbs Free Energy
Gibbs free energy is a calculation involving both enthalpy and entropy values for
a system
o The change in Gibbs free energy determines whether a process is
spontaneous or nonspontaneous
G < 0: Reaction proceeds in forward direction (spontaneous)
G = 0: Reaction is in dynamic equilibrium
G > 0: Reaction proceeds in reverse direction (nonspontaneous)
Gibbs free energy depends on temperature; temperature-dependent processes
change between spontaneous and nonspontaneous depending on the temperature

Concept Summary 8
Solids
Solids are defined by their rigidity and resistance to flow
o Atoms are sufficiently condensed to allow intermolecular forces, which
hold the particles together and restrict their range of motion
o These forces include van der Waals forces, dipole-dipole interactions, and
hydrogen bonds
o Solids may have a molecular structure that is crystalline or amorphous
o Crystalline solids have a three-dimensional repeating lattice arrangement;
individual lattice arrangements are called unit cells
Amorphous solids do not have a lattice arrangement
Liquids
Liquids are considered fluids because they flow in response to shearing forces
and take the shape of their container
Liquids have some properties similar to those of solids
o Atoms are sufficiently condensed to allow intermolecular forces, which
hold the particles together and restrict their range of motion
o These forces include van der Waals forces, dipole-dipole interactions, and
hydrogen bonds
Liquids that can fully mix, like alcohol and water, are considered miscible
Liquids that cannot mix, like oil and water, are considered immiscible
Emulsions can be formed by the agitation of two immiscible liquids
Phase Equilibria
Phase Changes exist at characteristic temperatures and pressures
o Fusion, or melting,
and crystallization, or freezing or solidification, occur along the
boundary between the liquid and the solid phases
o Vaporization, or boiling, and condensation occur along the boundary
between the liquid and the gas phases
o Sublimation and deposition occur along the boundary between the solid
and gas phases
o At temperatures above the critical point the liquid and gas phases are
indistinguishable
o At the triple point all three phases of matter exist in equilibrium
The change in Gibbs free energy for phase changes in equilibrium is zero
Phase Diagrams
The phase diagram for a system graphs the phases and phase equilibria as a
function of temperature and pressure
o For a solution containing multiple components, it indicates the composition
of the liquid and vapor phases at different temperatures and pressures
Colligative Properties
Colligative properties are physical properties of solutions that depend on the
concentration of dissolved particles but not on their chemical identity
o Vapor pressure depression follows Raoult's law
o Freezing point depression and boiling point elevation are shifts in the
phase equilibria dependent on the molality of the solution
o Osmotic pressure is dependent on the molarity of the solution
o For solutes that dissociate, the van't Hoff factor is used in freezing point
depression, boiling point elevation, and osmotic pressure calculations
Equations to Remember









Concept Summary 9
Nature of Solutions
Solutions are homogenous mixtures composed of two or more substances
o They combine to form a single phase, generally the liquid phase
o Aqueous solutions are most important for the MCAT
Solute particles surround solvent particles via electrostatic
interactions in a process called solvation, or dissolution
o Most dissolutions are endothermic
o The dissolution of gas into liquid is exothermic
Solubility is the maximum amount of a solute that can be dissolved in a given
solute at a given temperature; it is often expressed as molar solubility
Concentration
Units of solution concentration include:
o Percent composition by mass = mass solute/mass solution 100%
o Mole Fraction = moles of solute/moles of solution
o Molarity = moles of solute/liters of solution
o Molality = moles of solute/kilograms of solvent
o Normality = number of equivalents/liters of solution
Solution Equilibria
Saturated solutions are in equilibrium for that particular temperature
The solubility product constant for a given solute at a given temperature is K
sp

Comparison of the ion product (I.P.) to K
sp
determines the level of saturation and
behavior of the solution:
o I.P. > K
sp
, the solution is supersaturated and a precipitate will form
o I.P. = K
sp
, the solution is saturated and there will be no change
o I.P. < K
sp
, the solution is unsaturated and if more solute is added it will
dissolve
The common ion effect decreases the solubility of a compound in a solution that
already contains one of the ions in the compound
o This is an application of Le Ch telier's principle to solutions
Equations to Remember






Concept Summary 10
Definitions
Arrhenius defined acids as species that dissociate to produce hydrogen ions and
bases as species that dissociate to produce hydroxide ions
Br nsted-Lowry defined acids as species that donate hydrogen ions and bases
as species that accept hydrogen ions
Lewis defined acids as electron-pair acceptors and bases as electron-pair donors
All Arrhenius acids and bases are Br nsted-Lowry acids and bases, and all Br
nsted-Lowry acids and bases are Lewis acids and bases; however, the converse of
these statements is not true
Properties of Acids and Bases
Water is an amphotericspecies because it behaves as both an acid and base
The water dissociation constant, K
w
, is defined as K
w
= [H
3
O
+
][OH

] = 10
14
at
298 K
o K
w
, like other equilibrium constants, is only affected by changes in
temperature
pH and pOH can be calculated given the concentrations of H
+
(H
3
O
+
) and
OH

ions, respectively; pH + pOH = 14 at 298 K
Strong acids and bases completely dissociate in solution
Weak acids and bases do not completely dissociate in solution and are commonly
assignedK
a
and K
b
values depending on whether they behave as acids or bases,
respectively
The Br nsted-Lowry theory defines a reactant-conjugate pair as a weak acid-
conjugate baseor weak base-conjugate acid
K
a
and K
b
can be used to calculate the initial concentration of a reactant in a given
equilibrium expression
Salt Formation
A salt is formed from a neutralization reaction in one of four ways:
o Strong acid + strong base
o Strong acid + weak base
o Weak acid + strong base
o Weak acid + weak base
Polyvalence and Normality
Acid and base equivalents are equal to one mole of hydrogen/hydronium ions or
one mole of hydroxide ions, respectively; for example, NaOH has 1 base
equivalent and H
2
SO
4
(sulfuric acid) has 2 acid equivalents
Amphoteric Species
Amphoteric/amphiprotic species are those that can behave as a Br nsted-
Lowry acid or Br nsted-Lowry base, depending on the nature of the solution; the
best example is water it can accept a hydrogen ion to become a hydronium ion,
or it can donate a hydrogen ion to become a hydroxide ion
Conjugate species of polyvalent acids and bases can also behave as
amphoteric/amphiprotic species
Titrations and Buffers
Titrations are used to determine the concentration of a known reactant in a
solution
The equivalence point is indicated by the midpoint of a vertical slope in a titration
curve; it is reached when the number of acid equivalents in the original solution
equals the number of base equivalents added, or vice versa
o Strong acid and strong base titrations have equivalence points at pH = 7
o Weak acid and strong base titrations have equivalence points at pH > 7
o Weak base and strong acid titrations have equivalence points at pH < 7
Indicators are weak acids or bases that have different colors in the protonated
and deprotonated states; changes in color are indicative of a reaction reaching
its end point
Multiple equilibria (i.e., K
a1
, K
a2
, K
b1
, K
b2
, etc.) and equivalence points are observed
inpolyvalent acid and base titrations
Buffer solutions consist of a mixture of a weak acid and its conjugate salt or a
weak base and its conjugate salt; they resist large fluctuations in pH
The Henderson-Hasselbach equation quantifies the relationship between pH and
pK
a
for weak acids and pOH and pK
b
for weak bases; when a solution is optimally
buffered, pH = pK
a
and pOH = pK
b

Equations to Remember



Concept Summary 11
Oxidation-Reduction Reactions
Oxidation is a loss of electrons and reduction is a gain of electrons; the two are
paired together in what is known as a redox reaction
To assign oxidation numbers, you must be familiar with the seven rules found in
the Oxidation-Reduction Reactions lecture from this chapter; this will help you
determine if the reactant species are acting as oxidizing or reducing agents in
the chemical reaction
To balance redox reactions, review the five-step process involved in balancing
charge and atoms for a redox reaction; the electrons transferred in each half-
reaction must cancel out when summing the oxidation and reduction halves
Electrochemical Cells
An electrochemical cell describes any cell where redox reactions take place; for
all electrochemical cells, the flow of electrons is from the anode to the cathode
Galvanic (voltaic) cells are nonrechargeable batteries; the reaction that takes
place in a galvanic cell is spontaneous
Cell diagrams are shorthand notations representing the reduction and oxidation
taking place in an electrochemical cell; a vertical line represents a phase boundary
and a double vertical line represents a salt bridge
Electrolyticcells are rechargeable batteries; the reaction that takes place in an
electrolytic cell is nonspontaneous
Concentration cells are a specialized form of a galvanic cell; the reaction that
takes place here goes to equilibrium and is spontaneous
The charge on an electrode is dependent on the type of electrochemical cell you
are studying
o For galvanic cells, the anode is negatively charged and the cathode is
positively charged
o For electrolytic cells, the anode is positively charged and the cathode is
negatively charged
Reduction Potentials and the Electromotive Force
A reduction potential quantifies the tendency for a species to gain electrons and
be reduced
o Standard reduction potentials are calculated under the standard
conditions of 298 K, 1 atm, and 1 M for all participating ions
Electromotive force (emf) is the difference in potential between two half-cells
under standard conditions
For galvanic cells, the sum of the reduction potentials of the two half-reactions is
positive; for electrolytic cells, the sum of the reduction potentials of the two-half
reactions is negative
Thermodynamics and Redox Reactions
Emf and Gibbs free energy are related by the equation G =
nFE
cell,
where n represents the moles of electrons exchanged and F is Faraday's
constant; this expression is also true under standard conditions
o When E
cell
is positive, G is negative, as in galvanic cells
o When E
cell
is negative, G is positive, as in electrolytic cells
The Nernst equation describes the relationship between the concentration of
species in a solution and emf
There exists a relationship between the equilibrium constant K
eq
and E
o
cell
under
standard conditions
o When K
eq
(the ratio of products over reactants) is greater than 1, E
o
cell
is
positive
o When K
eq
is a ratio less than 1, E
o
cell
is negative