Chemical Reactions

Friday Sept 4th

Big Ideas
The Big Overview of Metabolism
life-sustaining chemical transformations (thanks, Wikipedia!)

Gibbs Free Energy and Reaction Energetics

Predicting energetics of common biological reactions
The caveats that require extra thought esp. activation energy!

ADP

Usable
Energy
Output

ADP

Anabolism

ATP

Macromolecules
Carbohydrates
Proteins
Fats
Nucleic acids

Catabolism

Metabolism
Overview

Subunits
Sugars
Amino acids
Fatty acids
Nucleotides

ATP

Usable
Energy
Input

Gibbs Free Energy:

Reaction Energetics

G = H - TS
Diff. in Free Energy
Products - Reactants

Diff. in Enthalpy
Products - Reactants
Diff. in Entropy
Products - Reactants

Lets look first at S

Entropy
Disorder/chaos
2nd law of thermodynamics

Entropy Question
Amino acid + amino acid + amino acid
Which side has higher/lower Entropy? Why?
Is the S positive or negative:
for the forward (anabolic) reaction?
for the reverse (catabolic) reaction?

protein

Lets look next at H

Enthalpy
Potential Energy
1st law of thermodynamics

First: one atom and its electrons

Loosely held electrons those in
outermost shells or in covalent
bonds have the greatest energy.
Why? It requires potential energy
to hold the negatively charged
electrons away from the positively
charged protons in the nucleus.
Nucleus

1s
t

2n
d

3rd

Electron shells

Second: two atoms and

shared electrons
Sharing of electrons (in the outermost orbital)
takes them even further away from the nucleus.
Hence, even greater potential energy is
represented by electrons in bonds.

http://snews.bnl.gov/popsci/nuclear-energy.html

Enthalpy Question
Amino acid + amino acid + amino acid
Which side has higher/lower Enthalpy? Why?
Is the H positive or negative:
for the forward (anabolic) reaction?
for the reverse (catabolic) reaction?

protein

Putting the pieces back together

Diff. in Enthalpy
Products - Reactants

Diff. in Entropy
Products - Reactants

G = H - TS
Diff. in Free Energy
Products - Reactants
IF G is negative: reaction is exergonic (i.e. energy is released)
IF G is positive: reaction is endergonic (i.e. energy is required)

Gibbs Free Energy Question

Amino acid + amino acid + amino acid

protein

Which side has higher/lower Gibbs Free Energy? Why?

Is the G positive or negative:
for the forward (anabolic) reaction?
for the reverse (catabolic) reaction?

ATP

+G

More
More disorder
disorder (+S),
(+S),
less
less chemical
chemical energy
energy
in
in bonds
bonds (H).
(H).

Anabolism

ADP

Catabolism

G
Pictorially

Less
Less disorder
disorder (S),
(S),
more
more chemical
chemical energy
energy
in
in bonds
bonds (+H).
(+H).

ADP

ATP

G Graphically
a. Endergonic/Anabolic reaction
(Non-spontaneous)
Products

Amount of
energy required
(+G)

Reactants

b. Exergonic/Catabolic reaction
(Spontaneous)
Reactants

Amount of
energy required
(G)

Products

So
If G is negative:
The products have lower enthalpy and higher
entropy than do the reactants. (H and +S)
This is a catabolic reaction
This is an exergonic reaction

If G is positive:
The products have higher enthalpy and lower
entropy than do the reactants. (+H and -S)
This is an anabolic reaction
This is an endergonic reaction

Caveat #1:
Different bonds have different enthalpies
When electrons are shared, what matters is how
tightly/loosely electrons are held. Ultimately this
is a consequence of elctronegativity.
Nonpolar = equidistant from nuclei = loosely held
= higher potential energy
Polar = closer to one nucleus = tightly held
= lower potential energy

Advanced Enthalpy Question

which has higher/lower Enthalpy:
a pound of sugar or a pound of fat?
H
|

Caveat #2:
Exergonic reactions are
chemically spontaneous reactions
This is a different meaning of the word
than we mean in colloquial English usage.
Here, spontaneous means that the
reaction yields energy.
However, you may still need to add energy
to get the reaction started!

Thus, a more accurate

Gibbs Free Energy graph
Transition state

EA

Reactants

e.g. protein

Uncatalyzed reaction
Products

e.g. amino acids

Caveat #3:
Endergonic reactions are paired with exergonic reactions

Exergonic

Endergonic

ATP

Energy

Endergonic

Catabolism

+G

+G

Anabolism

ADP

ADP

G
ATP

Energy

Exergonic

Exam problems to look at:

From the 2014 Exam #1 (aka the
personal grooming products exam:
Question 2 (all)
Question 3C and 3D
Question 4A

From the 2013 Exam #1 (aka the ill

maple tree exam):
Question 1A, 1B, 1C
Question 2B