Overview
● Kinetics: study of rate of chemical reactions (how fast the reaction goes); not able to
study this the same way as other aspects of reactions are studied (i.e., whether or not they
will occur)
● Collision model: used to demonstrate reactions and their rates
● Reactions categorized depending on
5.1: Reaction rates
● To understand reactions, you need stoich, energetics, and rate
● Kinetics studies speed/rate of reaction
● Important because:
○ Understand rate of reaction to know if it will be calm/explosive and to produce
products
○ Ex:
■ Most reactions take place at 10^-12 s
● Rates
○ Given: aA→ bB
○ Rate=(-∆[A])/a∆t OR rate=(∆[B])/b∆t (both rates will be equal)
○ Unit for rates is M/s (molarity per second) → represents change in concentration
over time
5.2: Introduction to rate law
● When concentration of a reactant rises, rate of reaction increases
● Rate law: used to quantify the change in the speed of a reaction; defined as:
○ R = k[A]^n[B]^m…
○ R is rate of reaction
○ k is the rate constant
○ A and B are reactants; brackets mean molarity
○ N and m are reaction orders
● Reaction Order
○ n and m define reaction order of respective reactants
■ Used to quantitatively determine speed of reaction
○ Describes by what factor the rate will increase
○ Total reaction order: sum of all of the reactant’s reaction orders
● Experimentally Determining Rate Law
○ In order to establish:
■ Take two experiments that are run in which one reactant is changed and all
others are held constant
■ Divide the first concentration by the second concentration to get a ratio (x)
■ Divide the first rate by the second rate to get a ratio (y)
■ Take the logxy to find the order of the reaction in respect to that reactant
● Rate Constant
○ Serves as a proportionality constant; it is temperature specific
○ Units also change depending on the rate order
● Rate Order
○ Zero Order Reaction
■ Independent of reactant concentration; always constant at given temp.
■ rate=k
■ Graph is equal to slope of -k
○ First Order Reaction
■ Differential rate law: Rate=k[A]
■ Uses ln to create a linear graph comparing concentration and tim
(integrated rate law) slope of line given by y=-k andy intercept is ln[A]0
■ Rate law:
● ln[A]1-ln[A]0=-kt
● [A]1=concentration of the reactant at time 1
● [A]0=initial concentration
● k=rate constant
● t=time passed
○ Second Order Reaction
■ Differential Rate Law: Rate=k[A]^2
■ Uses inverse to create a linear relationship between time and concentration
■ Rate law:
● (1/[A])-(1/[A]0)=kt
5.3: Concentration changes over time
● Measured by integrated rate law (change in concentration relating to time)
● The graphs used in kinetics are to represent the integrated rate law in a linear fashion
● Given: y=mx+b or y-b=mx:
○ First order
■ ln[A]1-ln[A]0=-kt
○ Second order
■ (1/[A])-(1/[A]0)=kt
● Physical Attributes
○ Affect reaction rate; pressure, volume, # of moles, temperature, and surface area
○ Pressure causes an increase in temperature→ increased kinetic energy
■ Increases reaction rate
○ Volume decreases the number of possible collisions because the particles become
more spread out
■ Decreases reaction rate
○ As concentration increases, so does rate; thus, proportional relationship with
number of moles
■ Increases reaction rate
○ Surface area of a reactant increases chance of collision
■ Increases reaction rate
● Given a graph of a reaction and asked to determine the order of the reaction:
○ Plug each concentration into the calculator using the following steps:
■ For zero order reactions:
● No work needs to be done; if it isn’t a straight line with slope -k
with the y axis being [A], it isn’t first order
■ For first order reactions:
● Take the natural log of [A] and notice the trend; it should be
steadily decreasing at a regular rate
■ For second order reactions:
● Take the inverse of [A] and notice the trend; it should be alinear
increase
5.4: Elementary reactions
● Elementary Reaction: single event reactions; there aren’t multiple steps to a reaction
(total reaction=elementary steps)
● Molecularity: number of molecules participating as reactants in an elementary reaction
● Unimolecular: single molecule involved
● Bimolecular: elementary reactions involving collision of two molecules
● Termolecular: elementary reactions involving simultaneous collision of 3 molecules;
very rare
● Rate law of an elementary reaction can be predicted from stoichiometric
coefficients/molecularity
○ Ex: given: A+B→product
■ Rate=k[A][B]
● Examples:
Elementary Step Molecularity Rate Law
A→ products Unimolecular Rate=k[A]
2A→ products Bimolecular Rate=k[A]^2
A+B→ products Bimolecular Rate=k[A][B]
2A+B→ products Termolecular Rate=k[A]^2[B]
A+B+C→ products Termolecular Rate=k[A][B][C]
●
5.5: Collision model
● Collision model: based on kinetic molecular theory; molecules must collide to react
○ Thus, greater collisions lead to greater reaction rates and anything increasing
collisions increases reaction rates; same applies in reverse
● Reaction occurs when reactants collide with sufficient energy (known as activation
energy or Ea)
○ Collisions that occur with enough energy to cause a reaction are known as
effective collisions
○ Otherwise called ineffective collisions
● Gaseous and aqueous reactants tend to react faster than solid reactants
○ Gases and liquids will increase rate of reaction with concentration
○ Solids have increased reaction rate when their surface area is increased (powders
react faster than chunks)
● Orientation of the molecules also matters; particles must collide in the appropriate
orientation for reaction to occur
5.6: Reaction energy profile
● Reaction progress expressed using graphs
●
● When reactant energy is greater than product energy→ exothermic
● When reactant energy is less than product energy→ endothermic
● Components of ReactionEnergy Profiles
○
○ Reactants
○ Activated complex: stage between reactants and products; transition stage
○ Products
● Arrhenius Equation
○ Relates temp dependence
5.7: Introduction to reaction mechanisms
● Reaction mechanism: process by which a reaction occurs
○ Describes order in which bonds are rearranged and new molecules are formed
○ Consists of a series of steps occurring in a sequence
● Elementary steps of a reaction added together result in the overall reaction and is
balanced
● While a reaction is occurring, the elementary steps produce an intermediate which is
completely consumed by the reaction and thus not written in the total reaction equation
○ Intermediate is neither a reactant nor a product
● Reaction mechanisms are speculation based on experimentation; MUST match these
criteria:
○ The sums of the elementary steps must equal overall balanced equation
○ Mechanisms must agree with experimentally determined rate law
● If the intermediate is a reactant in the slowest step, an equivalent value must be used to
substitute into the rate law
○ If the other step given is an equilibrium reaction, rate of forward reaction and
reverse reaction is equal
○ This can be used to solve for the concentration of the produced intermediate using
the equal concentration of the opposite side of the reaction
○ Then substitute this equivalent value into the rate law
● If there is another substance on the side of the intermediate:
○ Divide the concentration out of the equation so that the concentration of
intermediate is isolated and substitute the intermediate
5.8: Reaction mechanism and rate law
● Rate-determining step: slowest step of the mechanism constraints how fast a reaction
can go
○ Stoichiometric coefficients of this can then be used to determine rate law
○
5.9: Steady-state approximation
● Multistep reactions often have a rate-determining step which is much slower than the
other steps
○ steady -state approximation can be used to determine the rate law of the overall
reaction by using the elementary steps
○ Steady-state approximation: the assumption that a reaction intermediate is
produced and consumed at an equal rate, stating that aside from the start and the
end of the reaction, the concentration stays constant or in a “steady state” for the
duration of the reaction
● Overall rate law of reaction is determined by its slowest step
● Mechanisms are purely theoretical and are generated by chemists through the use of
experimental data
○ No reaction mechanism is absolutely true; it is simply more likely than the other
options
5.10: Multistep reaction energy profile
● Graphs of multistep reactions have an equal number of “bumps” to the number of steps
proposed
○ The highest bump is the slowest step
○ The lowest bump is the fastest step
● The space between the bumps is the intermediate
● The activation energy is the amount of energy required to pass the highest bump
●
● Note: because only the slowest step determines the activation energy, a catalyst would
only lower this bump; the rest of the profile remains the same
5.11: Catalysis
● Lower activation energy of a reaction; defined as species that are consumed in one step of
a reaction mechanism but appear again later
○ Go in as a reactant and come out as a product but remain untouched at the end of
the reaction
● No role in actual reaction; just modify the mechanism
○ In the overall reaction, written above the arrow
● Stated that the reaction is catalyzed by the catalyst
● Catalysts and Energy
○ Work by lowering activation energy
○ Decreases NOTHING else
○ May also work by splitting a one step high Ea reaction into a multistep low Ea
reaction
● Catalysts and Mechanisms
○ Reduce the number of steps in a multistep mechanism, meaning that the reaction
is completed at a faster rate
● How catalysts lower activation energy
○ Make orientation of colliding particles more likely to cause a reaction
○ Reducing number of steps by becoming an intermediate that lowers activation
energy
○ Essentially they can
■ Stabilize an existing intermediate
■ Cause the creation of a new intermediate
Remember:
● When reading energy profiles, read the DIRECTION of the reaction as well
○
● Calculating Relative Rate
○ Use stoichiometric coefficients (mole ratio) to convert the rate of
disappearance/appearance to a different substance
● The reaction rate of a reaction decreases with time as the concentration of the reactants
decreases
○ The rate is thus greatest at the initial point of a reaction
● There is NO relationship between activation energy and temperature; Ea can ONLY be
lowered using a catalyst
