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EXAMKRACKERS GENERAL CHEMISTRY

Radius of one nucleus is 10^-4 Angstroms


o 1 angstrom = 10^-10 meters
A nucleon (protons, neutrons) is made up of 3 quarks
1 electron charge unit = 1.6 *10^-19 coulombs
A stands for mass number, not atomic number. It is Z which stands for number of protons,
and thus, atomic number
One atomic mass unit (amu, or simply, u) is also called a Dalton
Hydrogen-1 = protium
Hydrogen-2 = deuterium
Hydrogen-3=titrium
6.022*10^23 atomic mass units = 1 gram
moles = grams/atomic weight
Each horizontal row is called a period
Each vertical row is called a group or family
Traits of metals
o Lustrous
o Malleableeasily hammered into thin strips
o Ductileeasily stretched
o Thermally conductive
o Electrically conductive
All metals except mercury exist as solids at room temperature
Nonmetals have lower melting points than metals and tend to form negative ions. Also, they
tend to form covalent oxides
Metals tend to form positive ions and ionic oxides
Elements in same family tend to have similar chemical properties, but hydrogen is an
exception to this rule
In nature, alkali metals only exist in compounds and react exothermically with water
Heavier alkaline earth metals are more reactive than lighter alkaline earth metals.
Alkaline earth metals are tougher than alkali earth metals. They tend to have higher melting
points and are harder and more dense
Hydrogen is definitely a nonmetal!
**The molarity of O2 is equal to the molarity of any other ideal gas at the same temperature
and pressure
o Density divided by molecular weight is molarity!!
Oxygens group is called the chalcogens
Halogens are highly reactive
Smaller atoms have less room to stabilize which makes them bond more strongly to water =
higher heats of hydration
Large atoms have d orbitals allowing for more than 4 bonds
Large atoms cannot easily form pi bonds
Small atoms make strong pi bonds due to overlap of p orbitals
When transition metals lose electrons, they FIRST lose from their s subshell and THEN from
their d subshell!
Cations are much smaller than neutral atoms and anions are larger than neutral atoms
Effective Z = average nuclear charge Z electrons between nucleus and electron in question
Zeff or effective nuclear charge increases going left to right and top to bottom on the periodic
table
Atomic radius increases from top to bottom
Ionization energy: the energy necessary to detach an electron from a nucleus
The second ionization energy is always much greater than the first
Ionization energy increases from left to right and from BOTTOM TO TOP
Electronegativity increases from left to right and from BOTTOM TO TOP AS WELL!
Electron affinity increases from left to right and from BOTTOM TO TOP AS WELL!
Electron affinities for noble gases are endothermic whereas electron affinities for other
elements are exothermic
Metallic character increases from right to left and from top to bottom
Noble gases do not follow the trends for electron affinity or electronegativity

Bond length: the point where the energy level is the lowest
Bond energy/bond dissociation energy: energy necessary to achieve complete separation
between atoms
No energy is ever released by breaking a bond
Glucose is 40% carbon by mass
If a cation is made from a nonmetal, it ends with ium, like ammonium
Cupric is copper 2+
Couprous is copper 4+
More oxygenated species will use the ate suffix
H2S: hydrogen sulfide
H2SO4: sulfuric acid
H2SO3: sulfurous acid
For binary compounds, name is given with element first which is farthest to the left and
lowest in the periodic table
Physical change:
o Melting
o Evaporation
o Dissolution
o Rotation of polarized light
Running to completion: moves to the right until at least one of the reactants is depleted
o If a reaction reaches equilibrium first, it will not run to completion
Limiting reagent is NOT the one for which we have the least. It is the one which would be
used up FIRST if the reaction had run to completion

These reaction types are not mutually exclusive


The naught symbol indicates standard state conditions
Solids may be crystalline or amorphous
Crystalline solids:
o Sharp melting point
o Very definite shape with repeating units of atoms, ions, or molecules
o Salts are ionic crystals
o Metallic crystals: single metal atom bonded together by delocalized electrons
Delocalized electrons allow the atom to effectively conduct heat and
electricity, and they also make them malleable and ductile
o Ice is a molecular crystal
o Network crystals are diamond and silicon oxide
Amorphous solids, such as glassSiO2have a melting point range
Principal quantum number, n:
o Designates the shell level
o The greater this number, the greater the size and energy
o For the representative elements, the principal quantum number is their period in the
periodic table
o For transition metals, the principal quantum number lags one behind the period
number
o For lantahanides and actinides, the quantum number lags 2 shells behind the period
Azimuthal quantum number, l:
o L = n -1 to 0
o Designates the subshell
o L=1 is the p subshell
o L = 0 is the s subshell
o Gives the shape of the subshell
Magnetic quantum number, m:
o From l to +l
o Designates the orbital in which the electron lies
Spin quantum number, ms:
o May have a value of either or -
Pauli exclusion principle:
o No two atoms have the same 4 quantum numbers
Number of total orbitals within a shell = n^2
Heisenberg uncertainty principle arises from the inherent uncertainty which exists in
attempting to place the exact position in space of a particle due to its dual wave-particle
nature. Uncertainty is on the order of Plancks constant. For MCAT, momentum is mostly
related to the position.
Hunds rule: each subshell must contain at least 1 electron, and unpaired electrons in orbitals
will have parallel spins
Wavelength = h/mv
In photoelectric effect, the minimum amount of energy required to eject an electron is the
work function
Kinetic energy = hf work
0 degrees Celsius and 1 atmosphere = STP
Mean free path: distance travelled by a gas molecule between collisions
All gases are miscible with one another, regardless of polarity
o However, given time and low temperatures, heavier gases will logically tend to settle
below lighter ones
It is possible to cool a gas by increasing its volume
When a gas expands, kinetic energy is lost
At STP, any one mole of gas will occupy a volume of 22.4 Liters, if it is behaving ideally
Kinetic energy = 3/2*R*T
o Also valid for liquids
o This is the average kinetic energy for a mole of gas molecules
Velocity1/velocity2=Square root(m2/m1)
Effusion rate 1/effusion rate 2 = Square root(m2/m1)
Diffusion is the spreading of one gas into another gas or into empty space
Volume decreases with increasing pressure or decreasing temperature
Low temperatures cause gas molecules to settle close together
Gases generally deviate above 10 atm and at temperatures near their boiling point
Volume of a real gas is greater than volume of an ideal gas
Real gas exerts less pressure than predicted by the ideal gas law
Negative deviation from PV/RT results from intermolecular forces, mainly
Positive deviation from PV/RT =1 results from molecular volume, mainly
Kinetics deals with reactions as they move towards equilibrium, whereas thermodynamics
deals with reactions after they have established equilibrium
o Kinetics tells how fast equilibrium is achieved, whereas thermodynamics tells us what
it looks like
The rate of ANY reaction increases with temperature
o This is because more collisions with sufficient relative kinetic energy occur
Elementary reaction occurs in a single step
Concentrations of intermediates are usually small as they are unstable and react as soon as
they are formed
The rate law may only be determined by experiment
Steps after the rate-determining step will make NO contribution to the rate law
A catalyst creates a new reaction pathway which typically includes an intermediate
A catalyst may lower the activation energy or increase the steric factor
A catalyst CANNOT alter the equilibrium constant, and it increases the rates of both the
forward and the reverse reactions
A heterogeneous catalyst is in a different phase from the reactants and products
Adsorption: the binding of molecules to a surface
A catalyst increases the energy of collisions
Reaction rates can be enhanced by increasing the surface area of the catalyst, as this allows
for more adsorption sites
A catalyst DOES NOT prevent the original reaction from proceeding, but adds another
alternate, better reaction
o However, typically the rate of the original reaction is negligible when compared to
the rate of the catalyzed reaction
Rate constant of a liquid is a function of the solvent and of the temperature
Equilibrium is the point of greatest entropy
Equilibrium constant, K = concentration of products ^ coefficients/concentration of
reactants^coefficients
o This equilibrium constant depends on temperature ONLY!
Do not use solids or pure liquids such as water in the law of mass action
The reaction quotient, Q, describes reactions not at equilibrium, whereas K describes
reactions which are at equilibrium
o Q is not a constant and can have any positive value
o If Q = K, the reaction is at equilibrium
o If Q is greater than K, the reverse reaction rate will be greater than the forward
reaction rate
o If Q is less than K, the forward reaction rate will be greater than the reverse reaction
rate
Three types of stress which obey Le Chateliers law:
o Cooling/heating of a reaction system
o Changing the pressure
o Addition or removal or a product/reactant
Haber process:
o All gas reaction
o Exothermic
o Creates heat
o N2 + 3H2=2NH3+heat
o If we add N2, the system tries to compensate by reducing the parital pressure of N2 in
the forward reaction
o If we add He (inert), the total pressure increases in the container, but there is no
change in equilibrium direction. There is no shifting
This is because this does not change the partial pressure of the other gases
The solubility of salts generally increase with increasing temperature, even if the reaction in
question is exothermic
Equilibrium WILL probably shift with temperature, but the DIRECTION of this shift is
dictated by thermodynamics
The activation energy does not change during the reaction
Macroscopic properties are described via:
o Extensive traits: proportional to the size of the system
Volume, number of moles
o Intensive traits: independent of the size of the system
Pressure, temperature
Path functions: work, heat
o Depend on the pathway utilized to reach a certain result
State functions are pathway-independent
Any energy transfer that is not heat is work
Conduction: transfer of thermal energy via molecular collisions, and this requires direct
physical contact
o In all cases, a fatter conduit contributes to flow, a longer one impedes flow, and rate
of flow depends upon a gradient
o The order in which we layer slabs, or blankets, does not affect the rate of conduction
Convection: ocean, air currents
o Thermal energy transfer via fluid movements
Radiation
o Only heat transfer that occurs through a vacuum
o Thermal energy transfer via electromagnetic waves
o Rate of radiation depends upon temperature and surface area
o An object that radiates heat faster also absorbs heat faster
o An object that is a more efficient radiator comes to equilibrium more quickly
o Dark colors radiate and absorb better than light colors, which tend to reflect
A system at rest may still be able to do PV work
o Constant pressure*change in volume
o No change in volume = no PV work
o Occurs when a gas expands against a force!!!
In a pressure-v-volume graph, the area underneath the curve is WORK
Change in energy E = Q + W
o This incurs the convention that work done ON the system is positive; if work done
BY the system is positive, the equation then becomes E = q-w
Temperature is kinetic energy/mole of gas molecules
Heat cannot be completely converted to work in a cyclical process
Heat engine converts heat to work
Qh = w+qc
o Heat entering engine is equal to the workd one by the engine added to the heat
leaving the engine
o This can be reversed to create a refrigerator
Work is not a state function, and thus we must know the pathway in order to calculate it
Thermodynamic efficiency describes what percent of input energy is converted into work
7 state functions (i.e. independent of the pathway taken to get there)
o Internal energy
Includes vibrational, rotational, translational, electronic, rest mass energy, and
intermolecular potential energy
Vibrational, rotational, and translational energies affect temperature
Internal energy = heat = heat energy = thermal energy
o Enthalpy
Enthalpy = U + PV
Enthalpy is measured in joules
Not conserved
ENTHALPY OF THE UNIVERSE IS NOT CONSTANT!!!
Depends only on temperature
Extensive property
Standard state : 25 degrees Celsius
Enthalpy of reaction = enthalpy of products enthalpy of reactants
For constant pressure, closed system, & PV work only:
Enthalpy = q (heat)
Pathway-independent
If enthalpy is positive: endothermic
If enthalpy is negative: exothermic
On an energy diagram, the increase in energy is the activation energy,a dn the
peak of the hill is the transition state where bonds are breaking and new bonds
are forming
Intermediates exist between the lumps BETWEEN!!
Catalysts do not affect enthalpy
Activation energy for an endothermic reaction is greater than that for an
exothermic reaction
Catalysts affect rate but DO NOT affect equilibrium
ENTHALPY OF A SOLID AT STP IS 0
o Entropy:
Natures tendency to create the most probable situation, which happens to be a
state of disorder
Second law of thermodynamics: entropy of an isolated system will never
decrease
Entropy change of forward reaction is equal to negative entropy change of the
reverse reaction
DICTATES THE DIRECTION OF A REACTION
Reactions at equilibrium have achieved maximum universal entropy
Entropy must increase in a reaction in order for such reaction to proceed
Entropy is an EXTENSIVE property and increase with number, volume, or
temperature
ENTROPY OF UNVIERSE WILL INCREASE IN A SPONTAENOUS
REACTION; ENTROPY OF SYSTEM MAY OR MAY NOT
o Temperature
o Pressure
o Volume
o Gibbs free energy
Is equal to enthalpy the product of temperature and entropy change
Best for constant temperature & constant pressure reactions
Equilibrium is when this change in Gibbs free energy is zeroconstant
temperature and pressure, reversible process, PV work only
If negative, increase in entropy and spontaneous reaction
Represents the maximum NON PV work that is available to be done by a
reaction
Extensive property
Non-conserved, in that an isolated system may have changing Gibbs free
energy
AT THE BOILING POINT OF A SUBSTANCE, GIBBS IS ZERO AS
SYSTEM IS IN EQUILIBRIUM

Zeroth law of thermodynamics: temperature exists
For an ide amdjl gas, the graph of volume-vs-temperature is exactly linear
Any increase in thermal energy also increases temperature
KE = (3/2)*k*T
Energy and number of moles are extensive properties
Temperature is an intensive property
Virtually all physical properties change with temperature
The greater the random translational kinetic energy of gas molecules per volume, the greater
the pressure
o PRESSURE IS AN INTENSIVE STATE FUNCTION
The most kinetically favored reaction is the one with the lowest activation energy
The largest energy drop is the one with the biggest energy drop
Entropy = heat/temperature
Change in entropy for an irreversible reaction is positive always
Solution: homogeneous mixture of two or more single compounds of a single phase, such as
solid, liquid, or gas.
Brass is solid solution of zinc and copper
In ideally dilute solutions, the mole fraction of the solvent is nearly 1
A colloid is like a solution, but with larger particles of solute
o Too small to be separated via filtration
o large and charged enough to be separated by a semipermeable membrane WORKS--
dialysis
o Hemoglobin, for example
o May be any combination of phases EXCEPT GAS AND GAS
o Foam, aerosol, emulsion, sol
o Foam is gas in liquid like whipped cream
o Aerosol is fog, smoke or solids in gas
o Emulsion is a liquid in liquid or solid (such as milk or butter)
o Sol is solid particles in a liquid like paint
o Colloidal suspensions will scatter light, in the Tyndall effect
True solutions will not do so
o solvent equivalent for colloids is called a dispersion medium
o May be lypophilic or lypophobic to this dispersion medium
Protein in water is lypophilic
Emulsified fat in water is lypophobic
o Adding heat or an electrolyte may cause coagulation
Ionic molecules are dissolved by polar substances
Solvation: when an ion is dissolved into its anions and cations

Weak electrolytes form few ions in solution
Molarity: moles of solute/volume of solution
Molality: moles of solute/kilograms of solution
Mole fraction: moles of solute/total moles of solute+solvent
Mass% = mass of solute/mass of solution *100%
Ppm = mass of solute/total mass of solution * 10^6
Normality: mass of acid or base that can furnish or accept one mole of protons
o A 1 molar solution of H2SO4 is 2 normal as it can donate 2 protons for each H2SO4
Heat of solution: heat needed to braek intermolecular bonds of solute + heat needed to break
intermolecular bonds of solvent + heat needed to form bonds between solvents and solutes
o First two steps are endothermic and last step is exothermic
If a reaction releases energy (i.e. is exothermic), this indicates that the ending intermolecular
bonds are stronger than the starting material. This is because the less energy a system has, the
more stable it is. The opposite is true for endothermic reactions
When a solution forms, entropy increases
Vapor pressure increases with temperature, as vaporization is an endothermic process
Boiling: when vapor pressure of the liquid equals atmospheric pressure
Melting: when vapor pressure of solid phase equals vapor pressure of liquid phase
Nonvolatile solution: solute with no vapor pressure
Negative heats of solution form stronger bonds and lower vapor pressure
In an ideal solution, the vapor pressure of the whole solution is somewhere between the
vapor pressures of either solute
When the rates of dissolution and precipitation are equal, the solution is said to be
SATURATED
In calculating the solubility product, always leave out pure liquids and solids
Solubility is the maximum number of the moles of solute that may be dissolved in a solvent,
not to be confused with the solubility product
For solubility, the order in which you add the solutes is irrelevant
A common ion added will shift equilibrium towards precipitation, but it will NOT affect the
solubility product
Compounds with nitrates, ammonium, and alkali metals are soluble, usually
Ionic compounds containing halogens are soluble except with silver, mercury, or lead
compounds, in which case they are insoluble
sulfates compounds are soluble except for lead, mercury, and heavier ALKALINE metals
heavier alkaline metals are soluble when paired with sulfides and hydroxides
carbonates, phosphates, sulfides, and hydroxides are generally insoluble, except for the above
cases when mentioned
pressure and temperature are factors which affect solubility
o pressure on a solid has little effect, but pressure on a gas does significantly influence
solubility
o solubility = k * P
P = vapor partial pressure of the gas in question
K = Henrys constant
C is solubility of the gas in moles/liter, typically
May also be written as:
Pressure (partial vapor) = K*mole fraction
AS TEMPERATURE INCREASES THE SOLUBILITY OF GASES DECREASES
Larger gases tend to be more soluble as they experience greater van der Waals forces
Common ion effect example: adding a strong base to a saturated solution of calcium
hydroxide causes more calcium hydroxide to precipitate, and this is because it shifts the
equilibrium ( Le Chateliers principle)
If a system is heated while at rest and no PV work is done, nearly all the energy goes into
raising the temoperature of the system
Heat capacity: a measure of the energy needed to CHANGE the temperature of a system
o C = q/delta T (largely used for heat capacity of entire system)
o Constant pressure heat capacity is greater than constant volume heat capacity
o Always POSITIVE on the MCAT; the heat added will always increase the
temperature
o Assume heat capacity does not change with energy, unless otherwise indicated
o Q = mc*delta T (largely used as specific heat capacity of a certain staetd substance)
o Specific heat of water = 1 calorie/gram*degree Celsius
Calorimeter: measures energy change
o Coffee cup calorimeter: measures energy change at constant pressure, which is
atmospheric pressure
Measures heat of reaction (change in enthalpy)
Q = change in enthalpy at constant pressure
Use q = mc*delta T
o Bomb calorimeter :
Measures energy changes at constant volume
Q=change in internal energy
During phase changes, the temperature does not change as the energy is going into breaking
the bonds that take the substance from one phase to another
Enthalpy change associated with melting: heat of fusion
Each phase of a substance has its own specific heat
Evaporation occurs when partial pressure above a liquid is less than the liquids vapor
pressure, but atmospheric pressure s greater than the vapor pressure
Entropy and enthalpy are both positive during melting and vaporization
Phase changes at constant pressure are governed by temperature
Triple point: point wherein substance can exist in equilibrium as a liquid, solid, and gas
Critical temperature: temperature above which substance cannot be liquefied regardless of
the pressure applied
o Pressure required to produce liquefaction at this temperature is called the critical
pressure
o Critical temperature and critical pressure together comprise the critical point
Supercritical fluid: beyond critical point and has characteristics of a fluid and a gas
On a heating curve, you can find the heat of fusion by measuring the length of the flat line
representing heat of fusion
Colligative properties depend on number, not kind
o Vapor pressure
o Boiling point
o Osmotic pressure
o Freezing point
Boiling point elevation equation:
o Delta T = k*m*i
M = molality
I = number of particles into which a single particle will dissociate when added
to solution
A substance boils when its vapor pressure = local atmospheric pressure
Molality does not change with temperature
MOLARITY does change with temperature
Osmotic pressure:
o Tendency of water or other solvent to move into solution via osmosis
o Osmotic pressure = i*Molarity*R*T
The smaller the cation and the higher the charge, the more acidic the substance is
pH = -logH+
pOH = -logOH-
pH + pOH = 14
many reactions in living cells involve the transfer of a proton
if there is an acid in a reaction, there must also be a base
the stronger the acid, the weaker its conjugate base.
The stronger the base, the weaker its conjugate acid
Bases taste bitter and are slippery
Amphoteric: may act as either an acid or a base

Polyprotic acids: may donate more than 1 proton


o Second proton donated is usually so weak that it has a negligible effect on the pH
Acids dissociate less in more concentrated solutions
Acid dissociation decreases with acid concentration, but acid strength increases with acid
concentration
More oxygens = stronger acid
Increasing bond strength and increasing polarity = decreasing acidity
Hydrides can be acidic, basic, or neutral
Hydride acidity increases to the right and down
Kw = 10^-14
pKw = 14 = pH + pOH
pka + pkb = 14
o in this law of mass action, pure solids and liquids are given a value of 1
Ka greater than 1 or pka less than 0 is indicative of a strong acid

Titration curve of strong acid by a strong base


For equally strong acid base titrations, the equivalence point is usually at pH = 7
o HWOEVER FOR STRONG ACIDS WHOSE CONJUGATE BASE IS A STRONG
ACID, THIS IS NOT THE CASE
Titration of weak acid with a strong base is shown below:

The half equivalence point is when exactly one half of the acid has been neutralized by the
base
o The concentration of the acid is equal to the concentration of the conjugate bae
o Also shows point in titration where solution is most buffered
Henderson-hasselbach:
o pH = pka + log(A-)/(HA)
a buffer is made from equal and copious amounts of weak acid and conjugate base
concentration of conjugate base at the equivalence point = number of moles of acid/(volume
of acid+volume of base used to titrate)
indicator is used to find the equivalence point
usually a weak acid whose conjugate base is a different color
when concentrations of a weak acid and its conjugate base are equal, the pH = pka, so to find
pH just take the log of Ka
transition metals change oxidation state according to the metals to which they are bonded
reducing agent gives electrons to an atom
o atom in the reducing agent is oxidized
o victim atom is reduced
reducing and oxidizing agents are compounds, not atoms
money metals except nickel do not oxidize spontaneously, meaning they have negative
oxidation potential values
o this means they do not oxidize easily
o this includes silver, copper, gold, platinum, mercury
the higher the electric potential the stronger the oxidizing agent
the lower the electric potential (more negative) the stronger the reducing agent
hydrogen has a reduction potential of 0
reducing and oxidizing are intensive properties do not multiply by coefficients etc
galvanic cell turns chemical energy into electrical energy
o also called a voltaic cell
o creates an electrical current
o must have an ionic conductor, usually in the form of a salt bridge, to prevent build up
of electrons on either side of the galvanic cell
o anode is negative and cathode is positive
electrons move towards the cathode, since opposites attract
o RED CAT AN OX
Reduction takes place at the cathode and oxidation takes place at the anode
o The cell potential (E) is also called electromotive force between the two terminals
when they are not connected
Drop in emf increases as current increases. Emf decreases as current increases
Cell potential for galvanic cell is always positive. There is always available
energy here to do work
o Concentrations are always 1M; REQUIREMENT FOR GALVANIC CELLS
o
This means that the anode contains platinum and zinc and the cathode
contains copper and platinum
o Positive cell potential indicates spontaneous reaction
Delta G = -nFE
N = moles of electrons transferred in balanced redox reaction
F = Faradays constant
E = EMF
work = (charge*voltage)
Negative delta G indicates work is being done BY the system, not ON
the system
o IN NONSTANDARD STATE CONDITIONS
Delta G = delta G standard + RT*lnQ
o At equilibrium, there is no energy available to do work; delta G = 0 at equilibrium
o Delta G standard varies with temperature (standard implying in a cell with 1M
concentrations
If K = 1, then delta G standard = 0 and equilibrium exists
If K is greater than 1, then delta G is less than 0
o Thus, if equilibrium constant (K) is greater than 1, the this reaction will proceed
spontaneously at standard state
If K is less than 1, then delta G is greater than 0
Only an electrolytic cell can have negative electric potential
A concentration cell always has nonstandard molarities and thus requires the Nernst equation
to solve
Galvanic cells are spontaneous
Electrolytic cell on the MCAT has negative EMF
o Here CATHODE IS NEGATIVE AND ANODE IS POSITIVE
o Yet reduction still takes place at cathode and oxidation still at anode
o In an electrolytic cell, electrons flow to the cathode
Since a concentration cell is a subtype of a galvanic cell in more limited form, its reactions
also always occur spontaneously
Current is coulombs/second
And current is also known as charge/second

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