Physics II: 4-6, 9-10 Flashcards
chemical mechanisms
propose a series of steps that make up the overall reaction
intermediates
molecules that exist within the course of a reaction but are neither reactants nor products overall
rate determining step
slowest step
limits the maximum rate at which a reaction can proceed
collision theory
rate of a reaction is proportional to the number of collisions per second between the reacting molecules
(not all collisions result in a chemical rxn)
collision theory
for a collision to be effective…
molecules must be in the proper orientation and have sufficient kinetic energy to exceed the activation energy
activation energy
Ea
minimum energy of collision necessary for a reaction to take place
collision theory eq
rate = Z x f
Z = total number of collisions occurring per second
f = fraction of collisions that are effective
arrhenius eq
A = frequency actor
R = ideal gas constant
frequency factor
A
aka attempt frequency
measure of how often molecules in a certain reaction collide
Arrhenius eq
relationship between freq factor and rate constant
direct relationship
as freq factor inc, rate constant inc
arrhenius eq
exponent relationship
as the exponent gets smaller, it becomes less negative -> increases create constant
arrhenius eq
what makes the negative exponent smaller? what does this do?
low activation energy and high temp -> inc rate constant
how to increase frequency factor
increase number of molecules in a vessel (opportunities for collision are increased)
transition state theory
states that molecules form a transition state or activated complex during a reaction in which the old bonds are partially dissociated and the new bonds are partially formed
from the transition state, the reaction can proceed toward products or revert back to reactants
transition state
have the highest energy (greater than reactants and products)
old bonds are weakened and new bonds begin to form
theoretical structures that cannot be isolated
free energy change of the reaction
ΔGrxn
difference between the free energy of the products and the free energy of the reactants
exergonic reaction
-ΔG
energy is given off
endergonic reaction
+ΔG
energy is absorbed
exergonic reaction diagram
endergonic reaction diagram
how do reaction concentrations affect reaction rate?
conc of reactants inc, number of effective collisions inc (frequency factor)
reaction rate will increase for all but zero order reactions
how does temperature affect reaction rate?
reaction rate inc, temp inc
bc temp is measure of particles’ avg kinetic energy
optimal temp for enzymatic reaction
35 - 40 C
how does the medium in which rxn takes place affect reaction rate?
depends on how reactants react w medium
polar solvents are preferred bc molecular dipole tends to polarize the bonds of the reactants,, thereby lengthening and weakening them, permitting the reaction to occur faster
how do catalysts affect reaction rate?
increase reaction rate without being consumed in the rxn
lowers activation energy for both forward and backward rxn
catalysts
increase reaction rate without being consumed in rxn
stabilize reactants so as to reduce the activation energy necessary for the rxn to proceed
homogenous catalysis
catalyst is in same phase as reactants
heterogeneous catalysis
catalyst is in a different phase from reactants
what do catalysts not affect?
free energies of reactants or products or difference between them
don’t change nonspontaneous rxns into spontaneous ones (only make spontaneous ones move quicker)
do not impact equilibrium position or measurement of Keq
how are rate laws determined?
experimentally
rate law eq
rate = k[A]x[B]y
aA + bB -> cC + dD
eq to determine the order of reactant A experimentally
Δrate = Δ[A]x
multiplication factors
zero order reaction
rate of formation of product C is independent of change sin concentrations of any of the reactants
zero order reaction
rate law
rate = k[A]0[B]0 = k
k units: M/s
ways to change the rate of zero order rxn
change temperature, add catalyst
zero order rxn graph
slope
conc vs time: linear, k = -slope
first order rxn
have a nonconstant rate that depends on the concentration of a reactant
first order rxn
rate law
rate = k[A]1
k units = s-1
radioactive decay
first order reaction
radiocative decay eq
[A]t = [A]0e-kt
first order rxn graph
conc vs time: nonlinear
ln[A] vs time: k = -slope
second order reaction
nonconstant rate that depends on the concentration of a reactant
second order rxn rate law
rate = k[A]1[B]1 OR k[A]2
k units = 1/Ms
second order rxn graph
conc vs time: nonlinear
1/[A] vs time: slope = k
mixed order reactions
have a rate order that changes over time
broken order reactions
have noninteger orders
mixed order rxn eq
mixed order rxn
k3[A] >> k2
first order wrt A
mixed order rxn
k3[A] << k2
second order wrt A
What equation can be used to give us the rate of a reaction (in general)?
HINT: Rate = change in _______ / change in ________.
Rate = change in concentration / change in time
True or false? The Rate-Determining Step is able to control the rate of the overall reaction by acting as a kinetic bottleneck, preventing the speed of the reaction being faster than the slowest step involved.
True. The Rate-Determining Step is able to control the rate of the overall reaction by acting as a kinetic bottleneck, preventing the speed of the reaction being faster than the slowest step involved.
Which of the following would NOT determine the rate of a reaction?
(A) The energy of the reagents
(B) The orientation of the colliding molecules
(C) The size of the reagents
(D) How frequently the reagent molecules collide
(C) The size of the reagents
The 3 main factors determining a reaction rate are:
I. The energy of the reagents
II. The orientation of the colliding molecules
III. How frequently the reagent molecules collide
reversible reactions
eventually reach state in which energy is minimized and entropy is maximized
dynamic equilibrium
forward and reverse reactions are occurring at a constant rate
law of mass action
gives the expression for equilibrium constant, Keq, and the reaction quotient, Q,
pure solids and liquids do not appear
reaction quotient
Q
calculated value that relates the reactant and product concentrations at any given time during a reaction
Keq
ratio of products to reactants at equilibrium
constant at a constant temp
describe entropy and gibbs free energy at equlibrium
entropy is at a max
gibbs free energy is at a min
Q < Keq
more reactants than products
rxn proceeds in forward direction
Q = Keq
dynamic equilbrium
reactants = products
forward rate = reverse rate
Q > Keq
more products than reactants
reaction moves in reverse direction
the larger the value of Keq…
the farther to the right the equilibrium position
when Keq has large negative exponent
negligible
when see icebox
skip the box and go straight the the Keq eq
le chatliers principle
if stress is applied to a system, the system shifts to relieve that applied stress
three main types of stresses applied to a system:
changes in: concentration, pressure and volume, and temp
increasing the conc of reactants or decreasing the conc of products will shift the rxn…
to the right
increasing the conc of products or decreasing the conc of reactants will shift the rxn…
to the left
what happens to a systems volume and pressure when a system is compressed?
volume decreases and pressure increases
what happens to a system’s volume and pressure when a system is decompressed?
volume increases and pressure decreases
increasing the pressure of a gaseous system (dec its volume) will shift the system…
toward the side with fewer moles of gas
decreasing the pressure of a gaseous system (inc its volume) will shift the system…
toward the side with more moles of gas
increasing the temp an endothermic rxn will shift the rxn…
to the right
decreasing the temp of an exothermic rxn will shift the rxn…
to the right
decreasing the temp of an endothermic rxn will shift the rxn…
to the left
Increasing the temp of an exothermic rxn will shift the rxn…
to the left
if a rxn is endothermic, heat functions as a __reactant/product__
reactant
ΔH > 0
if a rxn is exothermic, heat functions as a __reactant/product__
product
ΔH < 0
kinetic products
higher in free energy than thermodynamic products
can form at lower temps
fast products
kinetic products can form at __lower/higher__ temps
lower
thermodynamic products
lower in free energy than kinetic products
more stable
slower
Some reactions are known as being Irreversible. Explain how Activation Energy would make a reaction Irreversible.
The Activation Energy for the forward reaction is low enough to be achievable in nature, whereas the backwards reaction must have such a high activation energy that this reaction is unlikely to occur.
e^(-Ea / RT) is also known as the f. F is equal to 3.74⋅10^-3. What does that tell you?
This means that for every 1,000 collisions, 3.74 collisions will result in a successful reaction. The higher the f, the higher the success rate of reactions.
Increasing the Activation Energy will ____________ the frequency of successful collisions. Increasing the Temperature will ____________ the frequency of successful collisions.
(A) Increase, Increase
(B) Increase, Decrease
(C) Decrease, Decrease
(D) Decrease, Increase
(D) Decrease, Increase
Increasing the Activation Energy will decrease the frequency of successful collisions. Increasing the Temperature will increase the frequency of successful collisions.
What is the difference between a unimolecular and bimolecular reaction?
In a unimolecular reaction, one molecule participates in the reaction: A -> products.
In a bimolecular reaction, two molecules participate in the reaction: A + B -> products.
True or False? You can write the rate law for one-step (elementary) reactions simply based on the reaction formula (A + B -> C).
True. You can write the rate law for one-step (elementary) reactions simply based on the reaction formula (A + B -> C). When dealing with multi-step reactions, however, you will need to determine the rate law experimentally.