AP Chem Chpt 14 - Chemical Kinetics

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110 Terms

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Reaction Rate

The speed at which a chemical reaction occurs.

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Chemical Kinetics

The study of how fast chemical reactions occur.

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Reaction mechanism

Step-by-step pathway from reactants to products.

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direct

Relationship between Surface Area/Volume and Reaction Rates:

SArea/V+, RR+

(one factor impacting rates of reaction)

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direct

Relationship between concentration ([ ]) and reaction rates:

M+, RR+

(factor impacting rates of reaction)

(concentration+, probability of collision+ = rate+)

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direct

Relationship between temperature and reaction rates:

T+, RR+

(factor impacting rates of reaction)

(temp+, speed+, frequency & force of collisions+ = reaction rate+)

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more collisions

Why does an increase in temperature cause the reaction rate to increase?

(think about kinetic energy!!)

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catalyst

The presence/absence of a _______________ affects rates of reaction.

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Catalyst

Agent that speeds up a reaction without being used up (ex. enzyme).

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higher

The greater the frequency of collisions, the _______________ the reaction rate.

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A, reactant

Being used up in a reaction (disappearing)

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B, product

Being formed in a reaction (appearing)

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positive

Rates of disappearance and appearance are always ______________!!!

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Rate of disappearing

-∆[ ]/∆t

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Rate of appearance

∆[ ]/∆t

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M/s

Units for rates of disappearing/appearing.

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final - initial

∆ (change) =

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smaller

As a reaction progresses, there is a ________________ reaction rate due to decreasing concentration of reactants.

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directly

When volume is constant, moles and molarity are ______________ proportional.

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decreases

The average rate ______________ with time.

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Instantaneous rate

The rate at any instant in time.

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tangent, triangle

Instantaneous rate can be found by drawing a line __________ to the graph/points and then drawing a _______________.

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A → B

-∆[A]/∆t = ∆[B]/∆t

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2A → B

-1/2 ∆[A]/∆t = ∆[B]/∆t

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3A → 2B + C

-1/3 ∆[A]/∆t = 1/2 ∆[B]/∆t = ∆[C]/∆t

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increase

Rates ____________ when reactant concentration is increased.

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decrease

Rates ______________ as the concentration of reactants in reduced.

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Rate 1/Rate 2 = [A₁]^m [A₂]ⁿ/[B₁]^m [B₂]ⁿ

Equation to determine Rate Law:

1) Pick 2 experiments where [A] remains constant and [B] changes to find n.

2) Pick 2 experiments where [B] remains constant and [A] changes to find m.

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Rate Law

The overall concentration dependence of reaction rate.

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k

Rate constant

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Reaction orders

Exponents m and n in the Rate Law equation:

Rate = k[reactant 1]^m [reactant 2]ⁿ

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Overall reaction order

Sum of the reaction orders

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Yes

Are fractional or negative reaction order values possible?

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fast

A large value of k (10⁹ or greater) means the reaction is…

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slow

A small value of k (10 or lower) means the reaction is…

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no

If a reaction is zero order, will changing the initial concentration of the reactant have an effect on the rate?

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double

If a reaction is in First Order, doubling the concentration will cause the rate to…

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(2²)-fold

If a reaction is in Second Order, doubling the concentration will result in a ________ increase in rate.

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(3²)-fold

If a reaction is in Second Order, tripling the concentration will result in a _________ increase in rate.

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(2ⁿ)-fold

A reaction is nth order if doubling the concentration causes a _________ increase in rate.

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yes

Does the rate depend on concentration?

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no

Does the rate constant depend on concentration?

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yes

Is the rate constant affected by temperature and the presence of a catalyst?

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k

Zero Order Rate Law

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M/s

Zero Order units

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k[A]

First Order Rate Law

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s⁻¹ or 1/s

First Order units

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k[A][B], k[A]², k[B]²

Second Order Rate Law (3)

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M⁻¹s⁻¹ or 1/Ms

Second Order units

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linear

Of given graphs, the one with the _____________ line/slope is the reaction.

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ln[A]t = -kt + ln[A]₀

First Order Integrated Rate Law

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-k

Slope of First Order graph

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ln[A]₀

y-intercept of First Order graph

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1/[A]t = kt + 1/[A]₀

Second Order Integrated Rate Law

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k

Slope of Second Order graph

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1/[A]₀

y-intercept of Second Order graph

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Rate = k[A][B]

Reaction that is second order overall, but has first order dependence on A and B:

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zero-order

A _______________ reaction is one whose rate is independent of the reactant concentration.

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[A]t = -kt + [A]₀

Zero Order Integrated Rate Law

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-k

Slope of Zero Order graph

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[A]₀

y-intercept of Zero Order graph

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half life

(t 1/2) The time required for the concentration of a reactant to decrease to half its original value.

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indirect

Relationship between [A]₀ and t 1/2:

[A]₀ - , t ½ +

(The reaction rate slows down as [A] goes down, making the half-life longer)

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t 1/2 = 0.693/k

First Order Reaction Half Life Equation

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t 1/2 = 1/k[A]₀

Second Order Reaction Half Life Equation

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k = 0.02 d⁻¹

(TEST QUESTION) The decomposition of a certain pesticide is a first order reaction. The half-life of the pesticide in 32.5 days. Solve for the rate constant.

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first

The half-life or a ________ order reaction is independent of the initial concentration of the reactant.

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second

The half-life or a ________ order reaction is dependent on the initial concentration of the reactant.

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concentration, temperature

Rates of reaction are affected by _______________ and ______________.

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Collision Model

Helps to explain how rates of reactions are affected. Based on the Kinetic Molecular Theory!

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orientation, energy, frequency

3 things impacting Collision Model:

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orientation, energy

In order for a reaction to occur, the reactant molecules must collide in the correct _____________ and with enough ___________ to form products.

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orientation

HAVE to have proper ________________ to end up with a reaction!

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broken

In order to form products, bonds must be ____________ in the reactants.

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requires

Breaking bonds __________ energy.

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Activation energy

(Ea) The minimum energy required to initiate a chemical reaction (will vary with the reaction).

[The energy barrier between the starting molecule and the highest energy state found along the reaction pathway.]

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Endothermic

Reactions taking in (absorbing) energy.

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Exothermic

Reactions releasing energy.

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products

For endothermic reactions, the potential energy is higher in the _____________.

(Energy profile: reactants start low, products end high)

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reactants

For exothermic reactions, the potential energy is higher in the _____________.

(Energy profile: reactants start high, products end low)

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lower

For a reverse endothermic reaction, is the Ea higher or lower than in an endothermic forward reaction?

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higher

For a reverse exothermic reaction, is the Ea higher or lower than in an exothermic forward reaction?

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indirect

Relationship between activation energy and reaction rate:

Ea-, RR+

(can get to products more quickly!)

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endothermic

If a forward reaction is exothermic, the reverse reaction is…

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transition state

The species at the top of the barrier between staring molecule and highest energy state.

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∆E

The difference in energy between the reactants and products in an energy profile.

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no

Does ∆E impact reaction rate?

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Ea

_________ is the difference in energy between reactants and transition state (forward) or products and transition state (reverse).

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equal, greater than

Molecules that have an energy __________ or ________________ Ea have sufficient energy to react.

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temperature, increases

As we increase the ________________, the fraction of the population that has an energy equal to or greater than Ea ______________.

(more molecules can react)

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frequency

What does the Arrhenius Equation explain in terms of the Collision Model?

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3

Reaction rates obey an equation based on _______ factors.

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direct

Relationship between temperature and frequency (Arrhenius Equation):

T+, A+

molecules move faster → increased number of collisions

↑ temp, ↑ KE, ↑ force/frequency of collisions, ↑RR

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Reaction Mechanism

The process by which the reaction occurs.

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broken, formed

Mechanisms provide a picture of which bonds are ____________ and ___________ during the course of a reaction.

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Elementary reactions

Any processes that occur in a single step.

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Molecularity

The number of molecules present in an elementary step.

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unimolecular

Reactions involving only ONE molecule.

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bimolecular

Elementary reactions involving the collision of TWO molecules.

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termolecular

Elementary reactions involving the simultaneous collision of three molecules (statistically impossible in the real world).