Ch 14 - Chemical Equilibrium Flashcards
Equilibrium Constant
how far a chemical reaction goes based on an experimentally measurable quantity
What does a large equilibrium constant mean?
Nearly all reactants proceed to products
A reaction with can
reach an equilibrium
K
an equilibrium constant
Larger K value =
more reaction proceeds towards the products
Hb + O2 HbO2
- hemoglobin attached to blood and oxygen are an equilibrium process
- in the lungs O2 is high so reaction shifts right creating more HbO2 blood
- stores it with blood and move it to muscles
- in the muscles the oxygen is low and the Hb releases O2 to restore equilibrium
- hemoglobin binds oxygen when the surrounding concentration is high, but releases oxygen when the surrounding oxygen concentration is low
How does a fetus get O2 in the womb?
maternal and fetal circulation never mix but the fetal K is different allowing oxygen to be “handed off” from the mother circulation at very close proximity
Reversible
a reaction that can proceed in both the forward and reverse direction
Dynamic equilibrium
for a chemical reaction this is the condition in which the rate of the forward reaction equals the rate of the reverse reaction
Why in dynamic equilibrium products and reactants continue to
occur simultaneously but at the same rate
What is not true with dynamic equilibrium?
the products and reactants ARE NOT the same amount necessarily
Same rate NOT amount
As the amount of reactants goes down the amount of products goes up leading to
a slower rate of reactants(assuming non zero order rxn)
- the pool of reactants gets smaller
the rate of a reaction is direction proportional to the pool of reactants so as the pool decreases the rate goes down and likewise as…..
the amount of products increases the rate increases
- eventually the slow down of the rate of reactants and the speed up of the rate of products reaches an equilibrium
What is the equilibrium constant used for?
a way to quantify the concentrations of the reactants and products at equilibrium
Equilibrium Constant(K)
the ratio at equilibrium of the concentrations of the products raised to their stoichiometric coefficients divided by the concentrations of the reactants raised to their stoichiometric coefficients
Law of mass action
- K = ([C]^c[D]^d)/([A]^a[B]^b)
- products/reactants raised to their coefficients
K «_space;1(equilibrium to the left)
- reverse reaction is favored
- forward reaction does not proceed very far
- more reactants than products
K = 1(equilibrium in the middle)
- neither direction is favored
- forward reaction proceeds about halfway
K»_space; 1 (equilibrium to the right)
- forward reaction is favored
- forward reaction proceeds essentially to completion
- more products than reactants
reverse the equation, invert the equilibrium constant
- A + 2B 3C
- Kforward = [C]^3/([A][B]^2)
- 3C A + 2B
- Kreverse = ([A][B]^2)/[C]^3
- Kreverse = 1/Kforward
if you multiply the coefficients in the equation by a factor, raise the equilibrium constant to the same factor
- A + 2B 3C
- K = [C]^3/([A][B]^2)
- nA + 2n B 3n C
- K’ = [C]^3n/([A]^n[B]^2n)
= ([C]^3/([A][B]^2))^n
= K^n
If you add two or more individual chemical equation to obtain an overall equation, multiply the corresponding equilibrium constants by each other to obtain the overall equilibrium constant
- A2B
- K1 = [B]^2/[A]
- 2B 3C
- K2 = [C]^3/[B]^2
- sum: A3C
- Koverall = [C]^3/[A]
- Koverall = (K1)(K2)
- ([B]^2/[A])([C]^3/[B]^2)
= [C]^3/[A]
For gaseous reactions the partial pressure of a particular gas is….
proportional to its concentration.
Can the equilibrium constant be expressed in terms of the partial pressures of the reactants and products?
Yes
Kc = ([SO2]^2[O2]/[SO3]^2)
find Kp
Kp = ((Pso2)^2(Po2))/(Pso3^2)
Kp =
the equilibrium constant with respect to partial pressures
What is the difference with Kp compared to Kc?
Kp takes the form of the expression for Kc except it uses partial pressure for each gas in place of concentration
Kp = Kc(RT)^delta(n)
- R = .08206 (Latm/molK)
- T = temp kelvin
- delta n = change in moles of the reaction
- Product stoichiometric coefficient – reactant stoichiometric coefficient
- Kp = equilibrium constant with respect to partial pressure
- Kc = equilibrium constant with respect to concentration
as long as concentration units are expressed in molarity for Kc and atm for Kp you do not need to
write their corresponding units
- 1.5 M or 1.5 atm becomes 1.5
solids are not included in the equilibrium expression because their constant value is incorporated into the value of K
- the concentration of a solid DOES NOT change
- 2Co(g) CO2(g) + c(s)
- Kc = [CO2]/[CO]^2- similarly pure liquids are omitted from the expression
the most direct way to obtain an experimental value for the equilibrium constant of a reaction is to measure the
concentrations of the reactants and products in a reaction mixture at equilibrium
H2(g) + I2(g) 2HI(g)
- Kc = [HI]^2/([H2][I2])
- Kc = .78^2/(.11)(.11)
= 5.0 * 10^1
- always in M though not written(unitless)
ICE Table
A(g) 2B(g)
[A] [B]
- Initial 1.00 0.00
- Change -0.25 +0.50
- Equilibrium 0.75 0.50
K = [B]^2/[A] = .5^2/.75 = .33
reaction quotient(Qc)
the ratio – at any point in the reaction – of the concentrations of the products raised to their stoichiometric coefficients divided by the concentrations of reactants raised to their stoichiometric coefficients
When K and when Q?
- K at equilibrium
- Q not at equilibrium
the value of Q relative to K is a measure of the progress of the reaction toward equilibrium
- at equilibrium Q = K
Q < K
reaction goes to the right(towards products)
Q > K
reaction goes to the left(towards reactants)
Q = K
reaction is at equilibrium
ICE table with x
A(g) 2B(g) and K = 0.33
[A] [B]
Initial 1.0 0.0
Change -x +2x
Equil 1.0 – x 2x
- K = [B]^2/[A] = 2x^2/(1.0-x) = .33
= 4x^2/(1.0-x) = 0.33
Le Chatelier’s Principle
when a chemical system at equilibrium is disturbed, the system shifts in a direction that minimizes the disturbance
- a system at equilibrium tends to maintain equilibrium and bounces back when disturbed
What does a system do with disturbances?
when a system is disturbed the system reacts to counter the disturbance
3 main types of system disturbances
- change in concentration of a product or reactant
- change in volume or pressure
- change in temperature
Change in concentration of product or reactant:
N2O4(g) 2NO2(g)
Add NO2
if NO2 is added the reaction will shift left(proceeds in the reverse direction) consuming some No2 and creating more N2O4 to bring the NO2 concentration down until a new equilibrium is reached
- Before adding NO2: Q = K - Immediately after addition of NO2: Q > K - Reaction shifts left to reestablish equilibrium
Change in concentration of product or reactant:
N2O4(g) 2NO2(g)
Add N2O4
if N2O4 is added the reaction will shift right to reestablish equilibrium
- before adding N2O4: Q = K - Immediately after addition of N2O4: Q < K - Reaction shifts to right to reestablish equilibrium
Change in concentration of product or reactant:
increasing the concentration of one or more of the reactants(makes Q<K) causes
the reaction to shift to the right(in the direction of the products)
Change in concentration of product or reactant:
increasing the concentration of one of more of the products(makes Q>K) causes
the reaction to shift to the left(in the direction of the reactants)
Change in concentration of product or reactant:
decreasing the concentration of one or more of the reactants(makes Q > K) causes
the reaction to shift to the left(in the direction of the reactants)
Change in concentration of product or reactant:
decreasing the concentration of one or more of the products(makes Q<K) causes
the reaction to shift to the right(direction of the products)
The effect of a volume(or pressure) change on equilibrium
- a decrease in volume causes an increase in pressure
- an increase in volume causes a decrease in pressure
The effect of a volume(or pressure) change on equilibrium:
N2(g) + 3H2(g) 2NH3(g)
PV=nRT where lower mols of gas(n) = lower pressure(P)
- 4 mols on left and 2 mols on right - higher pressure will shift the system to the right to minimize the equilibrium disturbance - If the volume is increased then the equilibrium will more left converting 2mols back to 4 mols - what happens if an inert gas is added to increase the pressure? - NOTHING! The overall pressure increased but the partial pressures of the reactants and products did not change so equilibrium is not disturbed
The effect of a volume(or pressure) change on equilibrium:
decreasing the volume causes
the reaction to shift in the direction that has the fewer moles of gas particles
The effect of a volume(or pressure) change on equilibrium:
increasing the volume causes
the reaction to shift in the direction that has the greater number of moles of gas particles
The effect of a volume(or pressure) change on equilibrium:
if a reaction has an equal number of moles of gas on both sides of the chemical equation then
a change in volume produces no effect on the equilibrium
The effect of a volume(or pressure) change on equilibrium:
adding an inert gas to the mixture at a fixed volume has
no effect on the equilibrium
Exothermic Reaction
A + B C + D + heat
Endothermic Reaction
A + B + heat C + D
The Effect of a Temperature Change on Equilibrium:
at constant pressure(exothermic reaction) raising the temperature
of an exothermic reaction(adding heat) is similar to adding more product, causing the reaction to shift left(absorbing heat and producing more reactants)
- unlike adding more product the change in temperature will change the value of the equilibrium constant(add heat = smaller K)
The Effect of a Temperature Change on Equilibrium:
(exothermic reaction)at constant pressure, lowering the temperature causes
the reaction to shift to the right, releasing heat and producing more products
The Effect of a Temperature Change on Equilibrium:
endothermic reaction)at a constant pressure, raising the temperature(adding heat
causes the reaction to shift right to absorb the added heat
The Effect of a Temperature Change on Equilibrium:
endothermic reaction) at a constant pressure, lowing the temperature(removing heat
causes the reaction to shift left, form less products, and lowering the value of K
The Effect of a Temperature Change on Equilibrium:
in an exothermic chemical reaction
heat is a product
A + B C + D + heat
The Effect of a Temperature Change on Equilibrium:
In an endothermic chemical reaction
heat is a reactant
A + B + heat C + D
The Effect of a Temperature Change on Equilibrium:
increasing the temperature causes an exothermic reaction to
shift left(towards reactants); the value of the equilibrium constant decreases
The Effect of a Temperature Change on Equilibrium:
decreasing the temperature causes an exothermic reaction to
shift right(towards products); the value of the equilibrium constant increases
The Effect of a Temperature Change on Equilibrium:
increasing the temperature causes an endothermic reaction to
shift right(towards products); the equilibrium constant increases
The Effect of a Temperature Change on Equilibrium:
decreasing the temperature causes an endothermic reaction to
shift left(towards reactants); the equilibrium constant decreases