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Princeton Chemistry > Kinetics and Equilibrium > Flashcards

Kinetics and Equilibrium Flashcards

1
Q

kinetics

A
  • how reactions take place and how fast they occur
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2
Q

reaction coordinate

A
  • reactants
  • products
  • intermediates
  • steps
  • transition state
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3
Q

reaction rate

A
  • rate law
  • experimental data
  • change in concentration/time
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4
Q

in order for a reaction to occur

A
  • the reactants must collide
  • with the proper orientation
  • with a minimum energy (activation energy)
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5
Q

what is the middle hump in a reaction coordinate?

A
  • intermediate

- thermodynamic quantity

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6
Q
  • what are the two humps in a reaction coordinate?
A
  • transition states

- kinetic quantities

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7
Q

catalyst

A
  • not used up in the reaction
  • regenerates itself
  • does not affect intermediate
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8
Q

rate limiting step

A
  • highest peak or slowest slep
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9
Q

reaction rate formula

A

rate = -1/r (Δ[R]/Δt) = +1/p (Δ[P]/Δt)

r=reactant
p=product

  • rate reactants used up
  • rate products formed.
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10
Q

rules for rate laws

A
  • only uses reactants
  • reverse reaction not considered
  • no pure solids or pure liquids
  • n1 +n2 + n3 = reaction order
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11
Q

rate constant

A
  • proportional to the probability that a collision will result in a successful reaction

k=Ae^(-E_a/RT)

  • indirectly proportional to activation energy
  • directly proportional to temp and A
  • NOT AFFECTED by concentration of reactants.
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12
Q

equilibrium

A
  • achieved when forward rate = reverse rate
  • does NOT tell us reaction rate
  • reaction has not stopped
  • THERMO not kinetic
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13
Q

equilibrium constant

A
  • ratio of equilibrium product and reactant concentrations

Keq = [product]^P/[reactants}^R

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14
Q

equilibrium rules

A
  • concentration of each species is in equilibrium
  • constant ratio of products to reactants at a given temp
  • no pure solids and liquids
  • all capital K calculated the same way
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15
Q

K>1

A
  • in equilibrium favoring products
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16
Q

K=1

A
  • in equilibrium favors neither
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17
Q

K<1

A
  • in equilibrium favoring reactants
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18
Q

reaction quotient

A
  • Q
  • concentrations when reaction is not at equilibrium
  • value calculated using initial concentrations
  • depends on temperature and concentration
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19
Q

Q>K

A
  • NOT in equilibrium
  • reaction runs in reverse
  • excess of product
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20
Q

Q=K

A
  • in equilibrium
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21
Q

Q

A
  • NOT in equilibrium
  • reaction runs forward
  • excess of reactant
22
Q

Free energy and reaction quotient

A

ΔG = ΔG^o + RTlnQ

23
Q

Free energy and equilibrium constant

A

ΔG^o = -RT*lnKeq

24
Q

LeChatelier Principle

A
  • a system in equilibrium when stressed will shift in order to minimize that stress
25
Q

add a catalyst how does the reaction change?

A
  • it does not!
26
Q

volume effects

A
  • changing pressure stresses an equilibrium if the number of moles of gas changes in the reaction
27
Q

increase pressure by decreasing volume

A
  • shift to side with less moles of gas
28
Q

decrease pressure by increasing volume

A
  • shift to side with more moles of gas
29
Q

if a reaction is endothermic

A
  • treat heat as a reactant
30
Q

if a reaction is exothermic

A
  • treat heat as a product
31
Q

respiratory equation

A

H2O + CO2 = H+ + CO3 2-

32
Q

hyperventilating (increasing respiratory rate)

A
  • expel a ton of CO2
  • reaction runs to the left
  • use up more H+
  • blood becomes more alkalotic
33
Q

decreasing respiratory rate

A
  • hold onto more CO2
  • reaction runs to the right
  • produce more H+
  • blood becomes more acidotic
34
Q

formation equilibria

A
  • equilibrium of a coordination complex is a formation constant
  • reversing an equilibrium inverts the equilibrium constant
  • combining multiple equilibria results in the multiplication of the equilibrium constants
35
Q

solubility product

A

Ksp = [Sa+][Lt+]

36
Q

How to predict precipitation?

A

Compare Qsp to K

37
Q

Qsp>Ksp

A
  • not in equilibrium
  • you want to decrease the numerator so decrease the products
  • therefore run reaction in reverse and solid salt will precipitate
  • saturated
38
Q

Qsp=Ksp

A
  • in equilibrium
  • saturated
  • no more solute can dissolve
39
Q

Qsp < Ksp

A
  • not in equilibrium
  • you want to increase the numerator so increase the number of products
  • therefore run reaction in forward direction so more salt dissolves
  • unsatured
40
Q

common ion effect

A
  • a salt’s solubility will decrease if it is added to a solution containing a common ion
  • a salt’s solubility will increase if it is added to a solution containing something that removes a common ion
41
Q

Dissociation constant

A

k2/k1=[A][B]/[AB]=Kd

42
Q

Affinity constant

A
  • the strength of binding of a molecule to ligand.

k2/k1=[A][B]/[AB]=Kaff

43
Q

Relate Kaff to Kd

A

Kaff=1/Kd

44
Q

kinetics terms

A
  • rate
  • mechanism
  • catalyst
  • intermediate
  • transition state
  • activation energy
45
Q

thermodynamics terms

A
  • stability
  • equilibrium
  • spontaneity
  • energy
  • entropy
  • enthalpy
  • free energy
46
Q

only thing that affects both kinetics and thermodynamics

A
  • temperature
47
Q

transition states

A
  • non isolatable species
48
Q

intermediate

A
  • generated and used it

- detectable and isolatable

49
Q

raw law determined by

A
  • rate determining step
50
Q

what doesn’t affect position of the equilibrium

A
  • solids and liquids

- inert gases

Princeton Chemistry (6 decks)

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