MCAT Physical Chemistry: Equations and Important Facts

Lecture 1: Atoms, Molecules, and Quantum Mechanics

-

Avogadros number = 6.022 1023

Cations are smaller than the original ions; anions are larger than the original ions
Five periodic trends
o Ionization energy, electron affinity, and electronegativity increase from left to
right, bottom to top
o Atomic radius and metallic character increase from right to left, top to bottom
Percent yield = 100 (actual yield/theoretical yield)
Quantum numbers
o Principal quantum number, n, designates the shell level
o Azimuthal quantum number, l, designates the subshell
o Magnetic quantum number, ml, designates the precise orbital of a given subshell
o Electron spin quantum number, ms, designates the spin number ( and -)
Pauli exclusion principle states that no two electrons in the same atom can have the same
four quantum numbers
Heisenberg Uncertainty Principle states that there exists an inherent uncertainty in the
product of the position of a particle and its momentum; x p h
Aufbau principle states that with each new proton added to create a new element, a new
electron is added as well, to the lowest energy orbital available
Hunds rule states that electrons will not fill any orbital in the same subshell until all
orbitals in that subshell contain at least one electron, and the unpaired electrons will have
parallel spins
Plancks quantum theory: E = hf, Ephoton = hf, Plancks constant = h = 6.63 10-34 J s

Lecture 2: Gases, Kinetics, and Chemical Equilibrium

-

Standard temperature and pressure, STP is 0C or 273 K, and 1 atm

Mean free path is the distance traveled by a gas molecule between collisions
Kinetic molecular theory, characteristics of an ideal gas
o Gas molecules have zero volume
o Gas molecules exert no forces other than repulsive forces due to collisions
o Gas molecules make completely elastic collisions
o The average kinetic energy of has molecules is directly proportional to the
temperature of the gas
Ideal gas law: PV = nRT, universal gas constant = R = 0.08206 L atm/K mol = 8.314 J/K
mol
At STP, one mole of gas, behaving ideally, occupies the standard molar volume of 22.4
liters
Partial pressure: Pa = Xa Ptotal
Daltons law: Ptotal = P1 + P2 + P3 +
KEavg = 3/2 RT
Grahams law: v1/v2 = m2/m1

Effusion is the spreading of a gas from a high pressure to a very low pressure through a
pinhole (opening much smaller than the average distance between gas molecules
o Effusion: effusion rate1/effusion rate2 = M2/M1
Diffusion is the spreading of one gas into another gas or into empty space; can be
calculated much like effusion rates
Real gases deviate from ideal behavior when their molecules are close together
o High pressures, low temperatures cause more deviations; generally deviate at
pressures above ten atmospheres and temperatures near their boiling points
o Vreal > Videal, where PVideal = nRT
o Preal < Pideal, where PidealV = nRT
Two requirements for a given collisions to create new molecules in a reaction
o The relative kinetic energies of the colliding molecules must reach a certain
activation energy
o The molecules must have proper spatial orientation
The rate of a reaction increases with temperature mainly because more collisions with
sufficient energy occur each second
Elementary reactions are those that occur in a single step
Intermediates are species that are products of one reaction and reactants of a later reaction
in a chain
Balanced equation: aA + bB cC + dD
o Rate law: rateforward = kf [A][B], where and are the orders of each respective
reactant and the sum of + is the overall reaction order
o If the reaction is elementary, = a and = b
Irreversible first order reaction: A products, rate = kf [A]
o A graph of ln[A] and time t gives a straight line with a slope of -kf
Irreversible second order reaction 2A products, rate = kf [A]2
o A graph of 1/[A] and time t gives a straight line with a slope of kf
Second order reaction A + B products, rate = kf [A][B]
o Does not have same graph as other second order reaction
Irreversible third order reaction 3A products, rate = kf [A]3
o A graph of 1/2[A]2 and time t gives a straight line with a slope of kf
In any multi-step reaction, the slow step determines the rate
A catalyst increases the rate of the reaction without being consumed or permanently
altered; most work by lowering the activation energy
Equilibrium constant = Kc = [products]coefficients/[reactants]coefficients
Kp = Kc (RT)n, where n is the sum of the product coefficients minus the sum of the
reactant coefficients
Reaction quotient = Q = [products]coefficients/[reactants]coefficients
o If Q is equal to K, then the reaction is at equilibrium
o If Q is greater than K, there is a leftward shift towards the reactants
o If Q is less than K, there is a rightward shift towards the products
Le Chteliers principle states that when a system at equilibrium is stressed, the system
will shift in a direction that will reduce that stress
o Addition or removal of a product or reactant: adding a product or removing a
reactant favors the reactant side, and vice versa

o Changing the pressure of the system: increased pressure favors side with fewer
moles and vice versa
o Heating or cooling the system: heating favors the side without heat and vice versa
Lecture 3: Thermodynamics
-

The system is the macroscopic body under study, and the surroundings are everything
else
Three types of systems
o Open systems exchange both mass and energy
o Closed systems exchange energy but not mass
o Isolated systems do not exchange energy or mass
Extensive properties are proportional to the size of the system
Intensive properties are independent of the size of the system
Divide one extensive property by another to get an intensive property
State functions are pathway independent and describe the state of the system
Two ways to transfer energy between systems are heat q and work w
Heat has three forms
o Conduction is thermal energy transfer via molecular collisions; thermal
conductivity: Q/t = kA Th Tc/L; heat flow is constant across any number of slabs
between two heat reservoirs in a steady state system
o Convection is thermal energy transfer via fluid movements
o Radiation is thermal energy transfer via electromagnetic waves; StefanBoltzmann law: P = AT4, Stefan-Boltzmann constant = = 5.67 10-8 W/m2K4,
is the emissivity constant between 0 and 1
PV work is work done at constant pressure, w = PV
Work is path-dependent
The first law of thermodynamics states that energy of the system and the surroundings are
always conserved
o Energy change = E = q + w, w = work done on the system
The second law of thermodynamics states that heat cannot be changed completely into
work in a cyclical process
o Heat engines convert heat to work, a reversed heat engine is a refrigerator, which
requires work
o Carnot engines represent the most efficient engines possible, with efficiency = e =
1 TC/TH
Seven state functions
o Internal energy = U
o Temperature = T
o Pressure = P
o Volume = V
o Enthalpy = H
o Entropy = S
o Gibbs free energy = G
Internal energy is all the possible forms of energy imaginable on the molecular scale

In a closed system at rest with no electric or magnetic fields, the only energy change will
be in internal energy, U = q + w; this becomes U = q if there is no change in volume
and no work of any kind
The zeroth law of thermodynamics states that two systems in thermal equilibrium with a
third system are in thermal equilibrium with each other; defined temperature
Average kinetic energy of molecule in fluid: KEavg = 3/2 kT, Boltzmann constant = k =
1.38 10-23 J/K
Enthalpy is a man-made property that accounts for the extra capacity in a system at rest to
do PV work
o H U + PV
o H = U + PV, at constant pressure
For a pure liquid or solid, the standard state is a reference form of a system at any chosen
temperature T and a pressure of 1 bar or about 750 torr
An element in its standard state at 25C or 298 K has an enthalpy value of 0 J/mol
The standard enthalpy of formation, Hf, is the change in enthalpy for a reaction that
creates one mole of that compound from its raw elements in their standard state
For reactions involving no change in pressure, H = q
Heat of reaction: Hreaction = Hfproducts Hfreactants
Hesss law states that the sum of the enthalpy changes for each step is equal to the total
enthalpy change regardless of the path chosen
If H is positive, the reaction is endothermic; if H is negative, the reaction is
exothermic
Entropy is natures tendency toward disorder and its tendency to create the most probable
situation occur with a system
The second law of thermodynamics also states that the entropy of an isolated system will
never decrease
Ssystem + Ssurroundings = Suniverse 0
The third law of thermodynamics assigns by convention an entropy value of 0 J/K to any
pure substance at absolute zero and in internal equilibrium
S = dqrev/T
Gibbs free energy is an extensive property that represents the maximum non-PV work
available from a reaction
o If G is negative, the reaction is spontaneous and vice versa
G = H TS
o Positive H and negative S always results in positive G, and vice versa
o Positive H and S results in negative G at higher temperatures and vice versa
o Negative H and S results in positive G at higher temperatures and vice versa

Lecture 4: Solutions
-

A solution is a homogenous mixture of two or more compounds in a single phase

The compound of which there is more is called the solvent, and the compound of which
there is less is called the solute
Ideal solution are solutions made from compounds that have similar properties
Ideally dilute solutions are solutions in which the solute molecules are completely
separated by solvent molecules so that they have no interaction with each other

Nonideal solutions violate the conditions of both ideal and ideally dilute solutions
Particles larger than small molecules can form mixtures over time; if these do no settle
out due to gravity over time, this mixture is termed a colloidal system or colloid
o The Tyndall effect causes colloidal suspensions to scatter light
o Colloids can be separated via coagulation followed by filtration, or using a
semipermeable membrane, in a process called dialysis
Like solutes dissolve in like solutions, so that nonpolar solvents dissolve nonpolar solutes
and polar solvents dissolve polar solutes
Hydrogen bonds and dipole-dipole interactions hold together polar molecules
London dispersion forces hold together non-polar molecules via instantaneous dipole
moments
Solvation is the process by which ionic compounds break apart into cations and anions in
solution and are surrounded by oppositely charged ends of the polar solvent, called
hydration when water is the solvent
Something that is hydrated is said to be in aqueous phase
Electrolytes are compounds which form ions in aqueous solution; strong electrolytes
conduct electricity well and vice versa
Molarity = M = moles of solute/volume of solution
Molality = m = moles of solute/kilograms of solvent
Mole fraction = X = moles of solute/total moles of all solutes and solvent
Mass percentage = mass % = (mass of solute/total mass of solution) 100
Parts per million = ppm = (mass of solute/total mass of solution) 106
Normality measures the number of equivalents in solution
Formation of a solution
o The breaking of intermolecular forces between solute molecules
o The breaking of intermolecular forces between solvent molecules
o The formation of intermolecular bonds between solvent and solute molecules
Hsol = H1 + H2 + H3, where the first two steps are endothermic and positive, and the
third step is exothermic and negative; a negative value of Hsol results in stronger
intermolecular bonds, and vice versa
Solution formation has positive entropy
Vapor pressure is the pressure created by molecules that escape from the liquid phase into
the open space within a closed container
o Vapor pressures increases with temperature
o Boiling occurs when the vapor pressure of a liquid equals the atmospheric
pressure
o Melting occurs when the vapor pressure of the solid phase equals the vapor
pressure of the liquid phase
Raoults law: Pv = XaPa, applicable to a nonvolatile solute, which has no vapor pressure
Modified Raoults law: Pv = XaPa + XbPb, applicable to a volatile solute, which has a
vapor pressure
Negative heats of solution form stronger bonds and lower vapor pressure, and vice versa,
for nonideal solutions
Solubility is a solutes tendency to dissolve in solution
The reverse reaction of dissolution is called precipitation

o When the rates of dissolution and precipitation are equal, the solution is said to be
saturated, and is in dynamic equilibrium
Solubility product = Ksp = [products]coefficients/[reactants]coefficients, where the reactants and
products must be aqueous or gaseous
o The solubility product changes only with temperature
Some solubility guidelines
o Nearly all compounds containing nitrate (NO3-), ammonium (NH4+), and alkali
metals (Li+, Na+, K+,) are soluble
o Ionic compounds containing halogens (Cl-, Br-, I-) are soluble, except for silver
(Ag+), mercury (Hg22+), and lead (Pb2+)
o Sulfate compounds (SO42-) are soluble, except for mercury (Hg22+), lead (Pb2+),
and the heavier alkali earth metals (Ca2+, Sr2+, Ba2+)
o Compounds containing the heavier alkali earth metals (Ca2+, Sr2+, Ba2+) are
soluble when paired with sulfides (S2-) and hydroxides (OH-)
o Carbonates (CO32-), phosphates (PO43-), sulfides (S2-), and hydroxides (OH-) are
generally insoluble except in the cases mentioned above

Lecture 5: Heat Capacity, Phase Changes, and Colligative Properties

-

Heat capacity C is a measure of the energy change requited to change the temperature of
a substance
o C = q/T
Constant pressure capacity CP is greater than constant volume capacity CV
q = CT
Specific heat: q = mcT, c = specific heat of a substance
o cwater = 1 cal/gC
A coffee cup calorimeter is an example of constant pressure calorimeter because it
measures energy change at atmospheric pressure, also measures heats of reaction
A bomb calorimeter measures energy change at constant volume
Normal melting point and normal boiling point occur where a given substance changes
phase at 1 atm
Heat of fusion is the heat associated with melting, heat of vaporization is associated with
boiling
A phase diagram indicates the phases of a substance at different temperatures and
pressures
o There is only point where all three phases exist, called the triple point
o The critical temperature is the temperature above which a substance cannot be
liquefied regardless of the pressure applied
o The pressure required for liquefaction at the critical temperature is called critical
pressure
o The critical pressure and critical temperature define the critical point
Colligative properties are those that depend solely on the number of particles, regardless
of the type
Boiling point elevation: T = kbmi, vant Hoff factor = i = the number of particles into
which a single solute particle will dissociate into in solution
Freezing point depression: T = kfmi

Osmotic pressure: = iMRT

Lecture 6: Acids and Bases

-

An Arrhenius acid is anything that produces hydrogen ions in aqueous solution, and an
Arrhenius base is anything that produces hydroxide ions in aqueous solutions
A Brnsted-Lowry acid is anything that donates a proton, and a Brnsted-Lowry base is
anything that accepts a proton
A Lewis acid is anything that accepts an electron pair, and a Lewis base is anything that
donates an electron pair
pH = -log [H+]
The conjugate acid and base in a reaction correspond, respectively, the original base and
acid
The stronger the acid is, the weaker its conjugate base is, and vice versa
Kw = KaKb, Kw = 10-14
Amphoteric substances are those that can act as either acids or bases, depending on their
environments
Strong acids include hydroiodic acid (HI), hydrobromic acid (HBr), hydrochloric acid
(HCl), nitric acid (HNO3), perchloric acid (HClO4), chloric acid (HClO3), and sulfuric
acid (H2SO4)
Strong bases include sodium hydroxide (NaOH), potassium hydroxide (KOH), amide ion
(NH2-), hydride ion (H-), calcium hydroxide (Ca(OH)2), sodium oxide (Na2O), calcium
oxide (CaO)
Polyprotic acids are those than donate more than one proton
o In general, if the Ka values of the protons differ by more than 103, the second
proton can be ignored
Acid dissociation decreases with acid concentration but acid strength increases, because
although the relative percentage dissociation decreases, the absolute number of
dissociated ions increases
Factors in molecular structure that determine what hydrogen-containing compounds act
like acids
o The strength of the bond holding the hydrogen to the molecule
o The polarity of the bond
o The stability of the conjugate base
In a series of oxyacids, more oxygens means a stronger acid
Hydrides increase in acidity on the periodic table, from left to right and top to bottom
The autoionization of water is represented by H2O + H2O H3O+ + OHpH + pOH = pKw, pH + pOH = 14 at 25C
The acid dissociation constant Ka is the equilibrium constant of an acid in water
o For HA + H2O H3O+ + A-, Ka = [H+][A-]/[HA]
The base dissociation constant Kb is the equilibrium constant of the corresponding
conjugate base in water
o For A- + H2O OH- + HA, Kb = [OH-][HA]/[A-]
Salts are ionic compounds that dissociate in water
o All cations, except those of alkali metals and the heavier alkali earth metals, act as
weak Lewis acids in aqueous solutions

A titration is a drop-by-drop mixing of an acid and a base

The equivalence point for a monoprotic acid is the point in the titration when there are
equal equivalents of acid and base in solution
The half equivalence point is where exactly one half of the acid has been neutralized by
the base
o The concentration of the acid is equal to the concentration of its conjugate base
o Shows the point in the titration where the solution is most well buffered
o Here, the pH of the solution is equal to the pKa of the acid
Henderson-Hasselbalch equation: pH = pKa + log [A-]/[HA]
Indicators for pH change color at the end point of a titration

Lecture 7: Electrochemistry
-

In a redox reaction, electrons are transferred from one atom to another

o The atom that loses electrons is oxidized, and the atom that gains electrons is
reduced
Oxidation states
o Atoms in their elemental state have an oxidation state of 0
o Fluorine has an oxidation state of -1
o Hydrogen has an oxidation state of +1 normally, -1 when bonded to a metal
o Oxygen has an oxidation state of -2 normally, except in peroxides like H2O2
o Group 1 elements, alkali metals, have an oxidation state of +1
o Group 2 elements, alkali earth metals, have an oxidation state of +2
o Group 15 elements, nitrogen family, have an oxidation state of -3
o Group 16 elements, oxygen family, have an oxidation state of -2
o Group 17 elements, halogens, have an oxidation state of -1
The atom being reduced is also the oxidizing agent, and vice versa
There is an electric potential E associated with any redox reaction
o The oxidation and reduction components are individually referred to as half
reactions
o Each half-reaction can only have one electric potential and are usually listed as
either oxidation or reduction potentials in table; the signs of these values can be
reversed to find the value for the opposite half reaction
o 2H+ + 2e- H2, E = 0.00 V
o Reduction potentials are intensive properties, so half reaction potentials are not
multiplied by the number of times they occur
Galvanic, or voltaic, cells are used to turn chemical energy into electrical energy
o The two electrodes are called the cathode and anode, where reduction and
oxidation take place, respectively; also, the cathode is positive and the anode is
negative
o Current moves in the opposite direction of electrons, which move through the
load from anode to cathode
o In some types of galvanic cells, a salt bridge is used to minimize the potential
difference and prevent solutions from mixing and short circuiting the cell

G = -nFEmax, Faradays constant = F = 96486 C/mol, n = number of moles of electrons

transferred in the balanced redox reaction
A positive cell potential indicates a negative G and a spontaneous reaction
G = G + RT ln(Q)
o Also seen as G = G + 2.3RT log(Q)
G = -RT ln(K)
o If K = 1, then G = 0
o If K > 1, then G < 0
o If K < 1, then G > 0
Nernst equation: E = E - RT/nF ln(Q)
In a given concentration cell, current will flow from the more concentrated side to the
less concentrated side, in order to create more entropy
In an electrolytic cell, the cathode is negative and the anode is positive
o These cells are used for metal plating

Research Paper help

https://www.homeworkping.com/
o