Introduction to equilibrium

● Equilibrium expression is also called law of mass action or equilibrium law

● Many chemical changes are reversible
○ Represented by the double arrow (reaction moves in both directions)
● As the concentration of the reactant decreases, the rate of the reaction moving to the
products (right) decreases
● As the concentration of the product increases, the rate of the reaction moving to the left
increases
● Overall: rates of each reaction are dependent on its concentration
○ Collision theory: high concentration leads to high reaction rate
● As time goes on, the concentration of the product increases and the concentration of the
reactant decreases depending on the stoichiometric coefficient but levels off
○ Can be represented by a graph

○
● Dynamic Equilibrium: reversible reaction when the rate of forward reaction=rate of
reverse reaction
○ rate1=rate2
○ NOTE: concentrations do NOT need to be equal at equilibrium
Direction of reversible reactions
● Equilibrium is reached when the forward and reverse reactions occur at the same rate
○ Reversible reactions are always working towards equilibrium; natural tendency,
will reach there eventually
● Comparing Q and K can be useful in understanding the state of reaction and predicting
the direction of the reaction
○ When Q>K, reaction will move to the left
■ Calculated using [products]/[reactants]
 ■ If Q is too large, it means that there are too many products (increasing
numerator increases value of fraction)
○ When Q<K, reaction will move to right
■ If Q is too small, it means that there are too many reactants (increasing
denominator decreases value of fraction)
○ When Q=K, it is at equilibrium
Reaction quotient and equilibrium constant
● Equilibrium Constant: K; [products]/[reactants]; aka perfect equilibrium
○ KC=equilbrium constant for concentration
○ KP=equilbrium constant for pressure
○ NOTE: NEVER include solids/liquids in equilibrium constant expression
■ Replace this value with 1
● Reaction Quotient: Q; [products]/[reactants]; aka present state of reaction
○ Used to interpret the immediate state of a reaction and compare to K
Calculating the equilibrium constant
● Keq=[products]/[reactants]
○ Ex: 2A+B→A2B
○ Keq=([A2B])/([A]^2[B])
■ [] indicates molar concentration
○ Plug in the concentration of each species and solve for either the missing
concentration or K(or Q)
Magnitude of the equilibrium constant
● If K>1→ equilibrium lies very far to the right
○ The numerator (products) is far larger than the denominator
○ Thus, more products will be present
○ This also means that the reaction is thermodynamically favorable
● If K<1→ equilibrium lies far to the left
○ The denominator (reactants) is far larger than the numerator
○ More reactants are present
○ This also means the reaction is thermodynamically unfavorable
Properties of the equilibrium constant
● Manipulation of the equilibrium constant can be done sing its properties
○ Given the reaction: A+B→ C+D and K=([C][D])/([A][B])
○ The reverse reaction: C+D=A+B the equilibrium constant would thus be:
K=([A][B])/([C][D])
■ For a reverse reaction, take the inverse of K (1/K)
■ Note: a reaction that is thermodynamically unfavorable in one direction is
thermodynamically favorable in the reverse direction
 ○ If you multiply reaction by a coefficient: x( A+B→ C+D), then
K=(([C][D])/([A][B]))^x
■ When multiplying by a coefficient, raise K to the power of the coefficient
○ If you add reactions: multiply the two constants together
Calculating the equilibrium concentrations
● It is useful to organize data into an equilibrium table when calculating equilibrium
concentration
○ ICE Table: organizes the initial, change, and equilibrium concentrations of
species
● These tables can be used to calculate the concentrations of unknown values
○ When solving, the concentration of the reactant is likely provided
■ Assume that the concentrations of the products starts off as 0 unless
otherwise specified
○ The change is proportional to stoichiometric coefficients of each species
■ Thus, the change in concentration for the reaction 2AB→ 2A+B2 will be
-2x, +2x, and +x respectively
○ The equilibrium concentration will be the initial plus or minus the change
(reactants will be subtracted, products will be added)
● Two approaches exist to find these concentrations
○ small-K approximation
■ Assumes that the K value is so small that it is negligible
● In order for this to hold true, the following must be true:
● (initial change/[initial M])<5%
■ Ex:

○ large-K approximation
■ Takes into account K because it is too large ((initial change/[initial
M])>5%)
 ■ Ex:

■ Note: due to K’s large size, the reaction is treated as though it goes to
completion (thus the initial concentration of reactant is converted to
product using molar ratios and added while being subtracted from
reactant)
■ Note: when calculating for x, make sure to check both answers by
plugging back into the change; no concentration can be negative
Representations of equilibrium
● When given a model with particle representation, be able to calculate how many
molecules of each substance will be present at equilibrium
○ Count the number of molecules and solve using the similar method to the one
above (replace concentration with molecules)
○ K will be given in reference to molecules as well (an integer value)
● NOTE: make sure to keep the VSEPR model in mind when redrawing the molecules at
equilibrium
Introduction to Le Chatelier's Principle
● At equilibrium, forward/reverse reactions are equal
○ A shift in one direction means an increase in one of these rates
● Le Chatelier's Principle: when stress is placed on a system at equilibrium, system will
shift in response to stress
○ If shifted right: forward rate increases, more product
○ If shifted left: reverse rate increases, more reactant
● Concentration
○ When concentration of a species increases, reaction moves in direction to
consume excess species
■ If reactant is added, shift to right
■ If product is added shift to left
● Pressure
 ○ When external pressure is applied, partial pressures of each gas increase
■ This leads to the side with more gas molecules having more
concentration→ “excess”
■ Therefore, reaction shifts to side with less gas molecules
○ When pressure is relieved (decrease in pressure) partial pressures of each gas
decrease
■ This leads to the reaction shifting to the side with more gas molecules
○ If a gas is added to the reaction chamber (no necessarily a participating gas in the
reaction) the partial pressures of all the gases decreases
■ Therefore, shift to the side with less gas molecules
○ NOTE: if the moles of gas on both sides are equal, pressure will cause NO change
in rates
● Temperature
○ In order to understand the shift in reaction, thermodynamic quantities are used;
like species, energy also must be accounted for
■ In an exothermic reaction:
● Increasing temp (thus adding energy) reaction shifts away from
extra energy (products)
● Decreasing temp (thus taking away energy) would cause reaction
to generate sufficient energy (moving the reaction forward)
■ Opposite effect for endothermic reaction
● Dilution
○ Similar to the effect caused by changing volume for pressure
■ Removing water (via evaporation) causes reaction to shift towards side
with less species
● Less volume like increasing pressure
■ Adding water causes reaction to shift towards side with more aqueous
species
● More volume like decreasing pressure
Reaction quotient and Le Chatelier's Principle
● The shifts caused by pressure, concentration, and dilution are temporary and deviations
from K; will eventually reach K again
● Temperature shifts affect K; thus, ratio of products and reactants is affected
● Use reaction quotient, Q, to establish whether or not equilibrium exists and how to get
there
○ Calculated the same way as K but at non standard conditions
Introduction to solubility equilibria
● Low Ksp value indicative of insolubility
 ● High Ksp value indicative of solubility
Common-ion effect
● Common ion effect: when two substances share an ion and are dissolved in the same
solution, the concentration of the common ion will affect the solubility constant of the
salt whose Ksp is lower
● When calculating concentration of ions:
○ Make sure to substitute the concentration of the higher concentration of the ion in
the solubility product expression when calculating
○ Note: given coefficients, AB2(s)→ A(aq)+2B(aq):
■ Ksp=[A][B]^2
■ [A]=x
■ [B]=2x
■ Thus, when given the concentration of B, DON’T multiply by 2; that
concentration is given as already multiplied
pH and solubility
●
Free energy of dissolution
● ∆Gº=-RTlnK
○ R=gas constant, 8.31 J/mol*K
○ T= temperature (K)
○ K=equilibrium constant
● When ∆Gº is negative, K>1
○ Thermodynamically favorable
● When ∆Gº is positive, K<1
○ Thermodynamically unfavorable