Chem

XL-14C

Equilibria

!
! + !! ! + !
! [!]
! =!
! [!]

Product over reactant

Equilibria/Free Energy
Free energy indicates if a reac@on will happen

G = -RT lnK

If K > 1, reac@on goes forward to make products and G
is nega@ve

If K < 1, reac@on goes in reverse to make reactants and
G is posi@ve

-G is necessary for a reac@on to be spontaneous

Entropy/Enthalpy
Free energy is composed of two terms, Entropy
and Enthalpy

Entropy (S) is related to the degree of disorder,
and nature favors more disorder (Bigger +S)

Enthalpy (H) is related to the chemical energy of
bonding, nature favors forming stronger or
more bonds (Bigger H)

Entropy/Enthalpy
G = H T S
The change in free energy during a reac@on is
related to the change in Enthalpy and Entropy at
the reac@on temperature (in K)

H sign
S sign
G sign
Spontaneous?
-
+
-
always
+

never

-/+

At Low Temp

-/+

At high temp

Chemical Kine@cs

Acid/Base electron pushing

Head of arrow points toward where the electron
pair will move to.

Electron pair can be a bond or a lone pair.

Acid/Base Equilibria

Acid dissocia@on constant, Stronger the acid the bigger the K

pKa are the most common way of recording Ka in organic chemistry.

They are just the log. The more smaller the number, the stronger the acid

Acid/Base Strength
Acid strength depends mostly on the stability of the
conjugate base, A-. There must be some mechanism to
stabilize the nega@ve charge.

1) electronega@vity, some elements are able to stabilize
charge beZer due to their electronic congura@on (eg
F vs. C). Also leads to induc@on eects.
2) Ion size. Large atoms can distribute the charge beZer,
but also A-H is a weaker bond. (eg HF vs HI)
3) More resonance structures distributes charge over a
molecule, reducing charge on any single atom

Func@onal Groups

Bond Strength

!"#!!"!!"
!"#!!"!!"

= !
!"!!"#$%!!"#$%&
!"!!"#$%!!"#$%&

Carboca@on Stability
Hyperconjuga@on
Carboca@on (carbo cat ion)

Is a molecule that has a posi@ve charge on a
carbon

Carboca@on Stability
Hyperconjuga@on
Stability of carboca@on is ra@onalized similar to
conjugate base

Carboca@on Stability
Hyperconjuga@on

Alcohol Nomenclature
If there is an OH (hydroxyl) group, there is an
alcohol
Similar to alkane nomenclature
Except drop -e add -ol sux
Addi@onally number where the alcohol
appears, try to keep this number as low as
possible. (eg butan-2-ol)

Alcohol Nomenclature

Alcohol Nomenclature

Alcohol proper@es/ H-Bonding

Alcohols have high boiling points compared to their
alkane counter parts. That is due to hydrogen bonding

Alcohol/ Acids and Bases

Simple alcohols are about as acidic as water. The pKa values of most alcohols are of the order
of 18 (Ka = 10-18). Water has a pKa value of about 16 (Ka = 10-16). Recall that as pKa values
decrease (Ka values increase) the acidity increases. Subs@tuent groups can have a signicant
eect.

Rela@ve Acidity
MeOH > H2O > ROH > RC=CH > H2 > NH3 > RH
Except for methanol, most alcohols are slightly less acidic than water.

Alcohol/ Acids and Bases

Phenol is a stronger acid due to resonance

Spectroscopy
Light
Ioniza@on



Electronic transi@ons



Molecular vibra@on/rota@on


Electron spin ip



Nuclear spin ip

H-NMR
Nucleus is like electron in that there is spin.
Nuclear spin can be aligned or opposite of an
applied magne@c eld. Nucleus ground state
is to be aligned with eld.

Proton Chemical Shik

The frequency of radio waves necessary to
achieve spin ipping of the nucleus with a certain
strength of magnet, tells us about the
environment around the nucleus.
The electron cloud around a nucleus provides a
shielding eect. Which leads to a reduc@on in the
strength of the magne@c eld near the nucleus
Thus less energy is required to ip the spin of
shielded nucleus

Proton Chemical Shik

Low Field
Deshielded
Down Field

High Field
Shielded
Upeld

1
Proton Chemical Shik ( H-NMR)

Ethanol spectrum

1
Proton Chemical Shik ( H-NMR)

Chemical equivalence
On the @mescale of the NMR experiment, equivalent protons with respect to rota@on
are indis@nguishable

Chemical equivalence

Integra@on
Equivalent protons signal gives rise to larger
absorp@on
You can integrate a NMR spectrum to determine
the number of protons associated with a given
peak
Red line is integra@on (1:2:3)

ethanol

Splipng
The spin of a nearby nucleus aects the spin
of the measured nucleus

Splipng
N + 1 Rule

13C-NMR

More than 100 elements have nuclei with magne@cally ac@ve isotopes. They will
react measurably when exposed to magnet elds.

13C-NMR
13C has a nuclear spin that can be measured by NMR.
The abundance of 13C in a natural sample is low, as
most carbon is 12C
This leads to low signal for C-NMR
S@ll gives interes@ng informa@on
Spin-Spin coupling is removed, only informa@on is
nuclear spin

13C-NMR

MRI
Magne@c Resonance Imagining
is a 1H-NMR technique.
Protons in your body are
aligned. Dierent @ssues react
dierently to the magne@c
eld, and so it is possible to
contrast anatomy.

You'll no@ce that MRI dropped the word "nuclear." That's because people don't like
to hear the word "nuclear" when they're undergoing a medical procedure.
However, NMR has nothing to do with nuclear weapons or radioac@vity. It's called
"nuclear" because it deals with the nucleus of the atom.

MRI