Unit 3 Flashcards

1
Q

Chemical kinetics

A

describe how systems undergoing a chemical reaction change with time

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2
Q

Reaction rate

A

Rates of reactions can be determined by monitoring the change in concentration
of either reactants or products as a function of time. D[A] vs Dt
๐‘…๐‘Ž๐‘ก๐‘’ = ๐ถโ„Ž๐‘Ž๐‘›๐‘”๐‘’ ๐‘–๐‘› ๐‘๐‘œ๐‘›๐‘๐‘’๐‘›๐‘ก๐‘Ÿ๐‘Ž๐‘ก๐‘–๐‘œ๐‘› over
๐ถโ„Ž๐‘Ž๐‘›๐‘”๐‘’ ๐‘–๐‘› ๐‘ก๐‘–๐‘š๐‘’

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3
Q

Rate Law

A

an equation that shows how the reaction rate
depends on the concentration of each reactant.
ate = k[A]^m[B]^n
[A], [B] โ€“ conc. in M (or P)
k โ€“ rate constant
m โ€“ reaction order in A
n โ€“ reaction order in B
Reaction orders (thus rate laws) must be determined experimentally
Units of rate: M/s โ€˜[stuff] per secondโ€™
Units of k: โ€ฆdepend on the rate law expression

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4
Q

Integrated rate laws

A

are mathematical functions that give concentrations through time

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5
Q

The half-life

A

is the time it takes to react 50% of the reactants

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6
Q

The Arrhenius equation

A

describes how the rate constant changes with temperature

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7
Q

Reaction mechanisms

A

connect microscopic molecular processes to the overall rate
- Kinetics can reveal how a reaction occurs

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8
Q

Experimental determination of rate law

A
  1. Method of Initial Rates:
    The order of reactions (m, n) and the rate constant (k) are determined experimentally
    Experimental strategy -
    - change initial [B] while holding initial [A] constant and
    measure the new initial reaction rate each time;
    - then change initial [A] while holding initial [B] constant and
    measure the new initial reaction rate each time;
    - solve a system of rate law equations to determine the order
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9
Q

Graph method of rate law

A
  1. Graphical Method/ Integrated Rate Law
    Experimental strategy:
    - monitor the course of a reaction over time
    - plot data
    - shape of plotted line reveals order of reaction
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10
Q

zeroth order

A

straight line, decreasing slope.
RECOGNIZING Z EROTH ORDER REACTIONS
Plot the experimental [A] vs. time
If the graph is linear, the reaction is zero-order.
the rate constant k = (โ€’ slope)

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11
Q

zeroth order half life

A

Half-life: the time required for reactant concentโ€™n
to reach half of its original value
- dependent on the (initial) concentration
- gets shorter over the course of the reaction
(each successive half-life is half as long!)

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12
Q

First order

A

not linear, take the ln of it to know if the rxn is first order.
RECOGNIZING FIRST ORDER REACTIONS
Plot the experimental ln [A] vs. time. If the graph is linear, the reaction is first-order.
ยฎ the rate constant k = (โ€’ slope)

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13
Q

First order half life

A

t 1/2 is independent of the initial concentration
each successive half-life is an equal period of time โ†’ ๐‘ก1/2 is characteristic

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14
Q

Second order

A

Even more exponential than first order, take the reciprocal to get the slope.
RECOGNIZING A SECOND ORDER REACTION
Plot the experimental 1/[A] vs. time. If the graph is linear, the reaction is second-order.
ยฎ the rate constant k = slope

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15
Q

Second order half life

A

t 1/2 is dependent on the initial concentration
t 1/2 gets longer over the course of the reaction (each successive t 1/2 doubles in length)

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16
Q

REACTION MECHANISM

A

the step-by-step sequence of elementary reactions by
which reactants become product
- each step usually involves
only a small amount of
bond breaking/making.

17
Q

elementary reaction

A

describes an individual molecular event

18
Q

overall reaction

A

describes the reaction stoichiometry
the slowest step is called the rate limiting step

19
Q

REACTION INTERMEDIATE

A

a species that is formed in one step of a
reaction mechanism and consumed in a later step

20
Q

Molecularity

A

A classification of an elementary reaction based on the number
of molecules (or atoms) on the reactant side of the chemical equation

21
Q

UNIMOLECULAR REACTION:

A

an elementary reaction that
involves a single reactant
molecule.

22
Q

BIMOLECULAR REACTION

A

an elementary reaction that
results from an energetic collision
of two reactant molecules

23
Q

TERMOLECULAR REACTION

A

an elementary reaction that
involves three atoms or molecules.
RARE !

24
Q

Guess and Check to find mechanism

A
  1. Kinetics Experiment
  2. Propose a mechanism
  3. Compare experimental and predicted, they must be equal.
25
Q

Collision theory

A

Orientation factor (๐’‘) (a.k.a. steric factor)
Reactants must collide with the โ€˜correctโ€™ orientation
* 0 < ๐‘ โ‰ค 1
* ๐‘ for simple molecules is 0.001โ€’1
* ๐‘ can be < 10-5 for large molecules
* ๐‘=1 if the reaction is not sensitive to orientation

26
Q

Collision theory with rate constant

A

Collision theory: for a bimolecular reaction to take place, reactants A and B must
collide with proper orientation, and an energy greater than the activation energy Ea .
๐‘˜ = ๐‘๐‘๐‘“
๐‘ = fraction with correct orientation
Is it collision frequency (Z)?
f = fraction with
โ€˜sufficientโ€™ energy
๐‘ = collision frequency
k depends strongly on temperature
- one (or more!) of Z, p, f must depend on T
Z and f both do

27
Q

TRANSITION STATE

A

the unstable group of
atoms which represent the highest
energy species along the pathway from
reactants to products.

28
Q

ACTIVATION ENERGY

A

the minimum energy
required for a successful reaction

29
Q

Arrhenius equation

A

Ea is the activation energy
R is the ideal gas constant
๐‘˜ = ๐‘๐‘๐‘“ ๐‘“ = ๐‘’ ,-! //0
A (= Z p) is the frequency factor
(a.k.a. โ€˜pre-exponential factorโ€™)
higher T ยฎ smaller Ea /RT
ยฎ much smaller ex
ยฎ much larger reciprocal
ยฎ much larger k
ยฎ much increased rate

30
Q

Catalyst

A

A substance that provides an alternative reaction mechanism that is of
lower energy than the uncatalyzed mechanism ยฎ faster reaction!
- involved in the rate-determining step of the new pathway
ยฎ often appears in the rate law of the catalyzed reaction
- reacts early in the mechanism; regenerated later in the mechanism
ยฎ not consumed in the reaction; does not show up
in the overall reaction
- catalyzed reaction has the same endo/exothermicity as the uncatalyzed
reaction

31
Q

Enzymes

A

are catalysts of biological organisms, typically
protein molecules with large molecular weights
substrate enzyme complex