lecture 4 - chemical kinetics Flashcards

1
Q

arrhenius equation

A

k = A exp(- Ea / RT )

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2
Q

heating a reaction causes it to

A

go faster
increases its rate

temp has an exponential effect on k

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3
Q

what k in arrhenius equation

A

rate constant - varies with temp

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4
Q

what is A in arrhenius equation

A

pre exponential factor
same units as k

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5
Q

what is Ea

A

activation energy
J mol-1

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6
Q

what is R

A

gas constant

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7
Q

what is T

A

temperature
in K elvin

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8
Q

what is the arrhenius equation based on

A

empirical observations

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9
Q

another equation for arrhenius

A

k= A exp (-Ea/kB T)

Ea now has J units - Ea of an individual molecules, not a mole

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10
Q

activation energy

A

energy barrier that must be overcome when molecules collide in order for a reaction to occur

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11
Q

Ea units

A

kJ/mol

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12
Q

kinetics depends on

A

the Ea
not how exo/endothermic smt is

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13
Q

area under the curve

A

amount of particles

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14
Q

area under the curve after the Ea point

A

probability of a particle having the Ea.

shows the amount of particles that have the Ea or more

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15
Q

if temp stays the same but the Ea increases, what happens to the amount of molecules that have the Ea

A

it decreases

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16
Q

if the temp changes what happens to the graph

A

it changes
the distribution of energy changes

17
Q

low temp graph

A

tall and skinny

18
Q

high temp graph

A

wide and short

19
Q

when temp is increased, what happens to the amount of molecules that have the Ea

A

it increases

20
Q

exp (-Ea/RT) is proportional to what part of the curve

A

area under the curve past the Ea bit

this is where the temp dependence of the rate constant comes from

21
Q

what 2 things does the pre exponential factor depend on. A

A

frequency of collisions (determined using collision frequency)

probability of correct geometry of collisions for the reaction to occur

eg: frequency and orientation

22
Q

probability a collision will occur with the correct geometry is also known at the

A

steric factor

23
Q

what value do steric factors usually have

A

a very small number or 1

24
Q

what does steric factors having a small value mean/ represent

A

a very specific geometry is required

25
Q

what does a steric factor having the value of 1 mean

A

that any collision will lead to a reaction if it has the Ea required.
orientation/geometry doesnt matter

26
Q

what do we do to the steric factor and collision frequency to get the pre exponential factor, A

A

we multiply them together

27
Q

some reactions have multiple steps and the Ea and A correspond to 1 individual step however for k

A

may be a combo of individual rate constants ( combo of Ks)
or correspond to the K of the slowest step

28
Q

ln(k) = ln(A) - Ea/RT

A

plotting ln(k) against 1/T
gives straight line
gradient = -Ea/R
Ea = gradient x -R
intercept = ln(A)
then calculate A and Ea

29
Q

in some reactions, Ea changes with

A

temperature

due to changes in reactant structure + quantum mechanical tunnelling

30
Q

temp dependent Ea equation

A

Ea = -R d(ln((k)) / d(1/T)

31
Q

what does the arrhenius equation define

A

the rate constant ks temperature dependence