Midterm 1 Flashcards

(53 cards)

1
Q

What are substitution reactions?

A

One functional group substitutes for another

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2
Q

What is an elimination reaction?

A

Atoms or groups of atoms in adjacent carbons are eliminated as a small molecule
Saturated become unsaturated

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3
Q

What are addition reactions?

A

Opposite of elimination reactions

Double becomes single

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4
Q

What are nucleophiles and electrophiles?

A

Nucleophiles: attracted to positive charges (negatively charged)
Electrophiles: attracted to electrons (positively charged)
Most reactions happen when a nucleophile and electrophile interact

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5
Q

What are nucleophilic centres?

A

Lone pairs, negative charges, and multiple bonds

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6
Q

What are electrophilic centres?

A

Positive charges and positively polarized atoms

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7
Q

What are the two ways movement of electrons cause reactions?

A

1) a bond forms as a nucleophile and an electrophile interact (electrons in centre become barn)
2) bonding electrons move to an atom, breaking the bond, and the atom leaves

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8
Q

What occurs in nucleophilic substitution reactions?

A

A nucleophile attacks a substrate and creates a product and a leaving group

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9
Q

What are the two mechanisms of substitution reactions?

A

Sn2 - one step reaction where rate depends on concentrations of both
Sn1 - two step reaction. First step creates an intermediate carbocation which then reacts with the nucleophile. Rate is based on slowest step

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10
Q

What factors affect the SN1 reaction rate?

A
  1. Stability of the intermediate: tertiary is fastest

2. Strength of the leaving group: stronger bases = poor leaving group,

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11
Q

What are the two elimination mechanisms?

A

E2: rate depends on concentration of both, 1 step
E1: two steps, slow and fast

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12
Q

What is regioselectivity?

A

Placement of double bond
One is preferred over the other
Creates a major and a minor
The more highly substituted alkene is the major

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13
Q

What is stereo selectivity?

A

Cis or trans

Trans is generally major

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14
Q

How do you determine where the electronegative atom goes in an addition reaction?

A

Use markovnikovs rule: the less electronegative atom bonds to the C atom that have the greater number of H atoms

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15
Q

What occurs when you have chirality with addition reactions?

A

Nucleophile can attack from front or back so end up with 50/50 split S/R

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16
Q

Define spontaneous change

A

No action from outside the system is necessary
Occurs on it’s own
Naturally move only in spontaneous direction

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17
Q

Does spontaneous change = heat released?

A

Not always

Spontaneous change = energy released always

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18
Q

Define entropy

A

A measure of the disorder or randomness in a closed system
A quantitative measure of the amount of thermal energy not available to do work
The tendency for all matter and energy in the universe to evolve towards a state of inert uniformity

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19
Q

What is the Boltzmann equation?

A
S = k ln W
K= 1.38 x 10^ -23 j/k
W= number of ways that state can be achieved
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20
Q

Why is low energy less probable?

A

Nature is striving towards a state of high entropy

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21
Q

Is entropy a state or path function?

A

State function

Path taken and rate are irrelevant

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22
Q

When is entropy greater than 0?

A
Increase in enthalpy
Melting
Vaporizing
Making a solution
A reaction that produces an increased number of moles
Heating a substance
23
Q

Why is the entropy of melting greater than 0?

A

As goes from solid to liquid, becomes more disordered

24
Q

Why is the entropy of vaporizing greater than 0?

A

When going for liquid to gas, disorder increases

25
Why is the entropy of making a solution greater than 0?
It is far more likely that the solutions mix evenly than layered as it has a higher entropy
26
Why is the entropy of a redaction that produces an increased number of moles greater than 0?
More bonds are broken than made
27
What is the equation for calculating 🔺S of a solution?
🔺S rxn = E(vi Si) Vi = stochiometric coefficient of species i Si = absolute entropy of species i
28
When can the entropy of a system decrease?
Only if the entropy of the surroundings increases even more
29
What must the entropy be for the reaction to be spontaneous?
🔺S > 0
30
What is needed for a nonspontaneous process to take place?
Need outside action such as a change in p, T concentrations | Possibly but only if changing conditions
31
What is the equation for 🔺S of the surroundings?
-🔺H system / T
32
What is Gibbs free energy?
The maximum non-pV energy obtained from a system | 🔺G = 🔺H - T🔺S
33
When is Gibbs free energy greater than 0?
``` H S G spontaneous - + - always + - + never - - +- at lower T + + +- at higher T ```
34
Is free energy a state or path function?
State function | Path and rate is irrelevant
35
What is Q?
Reaction quotient | 🔺G = 🔺Go + RT ln Q
36
What happens to vapour pressure at equilibrium?
Rate of evaporation = rate of condensation
37
What is a Clausius-Clapeyron?
ln(pvap)=-(🔺Hvap/R)(1/T)+(🔺Svap/R)
38
What is a Clausius-Clapeyron pressure equation?
ln(p2) = ln(p1) + 🔺Hvap/R (1/t1-1/t2)
39
What is troutons rule?
🔺S'vap = 🔺H'vap/Tb
40
What is pyro metallurgy?
Production of metals from ores using heat
41
What are elementary reactions?
The simplest steps in a reaction Each involved bond making and breaking Usually unimolecular or bimolecular
42
What is the rate determining step?
The slowest elementary reaction in a multistep reaction | Determines overall rate of reaction
43
What does a catalyst do?
Speeds up a reaction but is not consumed itself | Provides a different mechanism for the reaction to proceed
44
What are the steps to heterogeneous catalysis?
1. Absorption 2. Migration across surface 3. Reaction 4. Desorption
45
What is a thermal explosion?
As reaction proceeds T rises, k rides Reaction goes faster t rises, k rises BOOM releases a large pressure wave
46
What is a chain explosion?
Radicals contain unpaired electrons which are very reactive 1. Initiation step: radicals are produced 2. Propagation steps: no net radical production than branching occurs, number of radicals increases More radicals = higher rates = more radicals = BOOM
47
What is the rate law?
Expresses how the rate varies with concentrations of reactants Rate = k[reactant]^n First order k= s^-1 2nd order k= M^-1 s^-1
48
What is the integrated rate law?
1st order: ln([A]/[A]o) = -kt | 2nd order: 1/[A] = kt + 1/[A]o
49
What is the half life?
1st order: t1/2 = 0.693/k | 2nd order: t1/2 = 1/k[A]o
50
What affects the reaction rate?
1. Rate of collisions between A and B 2. Fraction of collisions having correct orientation 3. Fraction of collisions having sufficient energy to cause reaction
51
What is the activation energy?
The energy required for a reaction to go to completetion
52
What so the Arrhenius equation?
K = Ae^-Ea/RT
53
What are the three most important types of organic reaction?
Substitution, elimination, addition