Week 12 LO27-28

Important note
• in revising LO27 and 28 in preparation for the
exam, please focus your study on the tutorial
notes provided here
 Units for enthalpy of reaction
• the LO very clearly states that the unit for
Enthalpy of Reaction is simply kJ
• however, multiple other sources state that the
unit is kJ/mol
• we will work with kJ/mol
not expressed
per mol
 Tutorial outline for LO27
• potential energy and change (Δ) in potential energy
• chemical energy as a type of potential energy
• chemical energy, covalent bonds and ATP
• making and breaking covalent bonds, heat (q) and
enthalpy (H)
• (ΔH) and exothermic vs endothermic reactions
• entropy (S) and ΔS
• Gibb’s free energy (G) and ΔG
• exergonic vs endergonic reactions
• ATP and reaction coupling
 Potential energy
• the energy an object has because of its situation
relative to some other object

low potential energy

high potential energy
 Potential energy
• the energy an object has because of its situation
relative to some other object

high potential energy

low potential energy

 Change (Δ) in potential energy
• the difference in potential energy relative to two
states (e.g. before and after)
 Chemical energy
• is a form of potential energy stored in
molecules (covalent bonds)
• the cell stores chemical energy in ATP and
glucose
• chemical energy can be converted to energy in
the form of heat, light, electricity or motion
(kinetic)
 Breaking and forming bonds
• breaking a bond uses energy (heat)
• forming a bond releases energy (heat)
• if the products release more heat than the
reactants consume, then the overall reaction
releases net heat and is exothermic
• if the products release less heat than the
reactants consume, then the overall reaction
releases net heat and is endothermic
 Chemical energy

reactants products

release absorption

Potential energy
of heat of heat
(exothermic) (endothermic)

products reactants
Chemical energy is stored in ATP

ATP + H2O

release

Potential energy
of heat
(exothermic)

ADP + Pi
 Heat (q) and and enthalpy (H)
• heat energy = q
• enthalpy (H) = total heat content of a system
• biological systems are under constant pressure and
volume
• therefore, in biological systems ΔH = Δq, in other
words, the change in enthalpy = the change in heat
energy
• also in biological systems, ΔH = ΔE; in other words, the
change in enthalpy = the change in internal energy
• ΔH = Δq = ΔE
 Change in enthalpy (ΔH)
• in biology, we are often specifically concerned with
the enthalpy of reaction, ΔHrxn
• ΔH = the net amount of heat absorbed in a reaction
• ΔH = heat used to break the bonds of the reactants
minus the heat released to form the bonds of the
products
• ΔH can be negative, meaning that, overall, heat is
released by the reaction = exothermic
• ΔH can be positive, meaning that overall heat is
absorbed by the reaction = endothermic
Chemical energy is stored in ATP

ATP + H2O
higher

ΔH is
negative

Potential
energy
ADP + Pi

lower
 Entropy (S)
• Entropy, S, is a measure of disorder or randomness
• the Universe tends toward increasing entropy (greater
disorder; ΔS is positive)
• think of your bedroom  ΔS is positive
• think of diffusion ΔS is positive
• every transfer of energy also increases the overall
entropy of the system
• increased entropy involves the release of energy as
heat
• diffusing skittles (beautiful entropy)
 Change in Entropy: ΔS
• a reaction in an isolated system will tend to
occur spontaneously when ΔS is positive (an
increase in disorder)
• but biological systems are not isolated
• neither ΔH nor ΔS will allow us to determine
whether a reaction will occur spontaneously
• so how can we determine if a reaction will
occur spontaneously?
 Gibbs’ Free Energy
• Gibbs’ free energy, G, allows us to determine
whether a reaction will proceed spontaneously
• all systems tend to minimize free energy (G)
• meaning systems tend to release free energy (go
to a lower free energy state)
• therefore a reaction is spontaneous if ΔG is
negative
• ΔG = Gfinal – Gstarting
• ΔG is negative if Gfinal is lower than Gstarting
 Exergonic vs Endergonic
• reactions with a negative ΔG (release of free
energy) are spontaneous and are called exergonic
• reactions with a positive ΔG (absorption of free
energy) are not spontaneous and are called
endergonic
• remember the terms exergonic and endergonic
are associated with ΔG (free energy)
• exothermic and endothermic are associated with
enthalpy (H), and do not predict spontaneity
 How do we determine ΔG?
• ΔG = ΔH – TΔS
• where T = temperature in degrees Kelvin
• T in many biological settings is constant
• another way to say it is that ΔG is the heat of
reaction minus that portion of the heat that is
due to changes
 Reaction coupling
• same as energy coupling
• how does the cell get non-spontaneous (+ΔG)
reactions to occur?
• it couples a reaction with +ΔG to one with a
–ΔG such that the net ΔG is negative
• in this way, the cell couples a non-spontaneous
process to a spontaneous one such that both
processes now take place, with the spontaneous
process driving the non-spontaneous one
An example of energy coupling: A hydroelectric dam

The Sayano–Shushenskaya Dam, Russia

An example of energy coupling: A hydroelectric dam

Water will flow downhill spontaneously, but the rotation of the turbines is
non-spontaneous. By placing the turbines in the path of the water flow, they
can be made to rotate. Thus, coupling the non-spontaneous process to the
spontaneous one allows the non-spontaneous process to proceed.
https://www.youtube.com/watch?v=rnPEtwQtmGQ (watch from 0:56 to 1:27)
 Hydrolysis of ATP is a
spontaneous reaction (–ΔG)
ATP + H2O
higher

ΔG is
negative

Potential
energy
ADP + Pi

lower
 ATP – the Biological Currency
• the hydrolysis of ATP to ADP + Pi is a reaction that
releases a large amount of free energy
• the conversion of ATP to ADP + Pi is highly exergonic
and spontaneous, with a large negative ΔG between
–30.5 and –65 kJ/mol
• therefore many non-spontaneous reactions in the
cell proceed because they are coupled to the
hydrolysis of ATP
• some reactions obtain energy from other NTPs; for
example peptide bond formation during translation
depends on the hydrolysis of GTP
 Why is ATP  ADP + Pi a spontaneous reaction?

γ β α

• same as asking why ATP  ADP has a large –ΔG (why it releases
a lot of free energy)
 Why is ATP  ADP + Pi a spontaneous reaction?

• remember: ΔG = ΔH – TΔS
– ATP is more ordered than ADP + Pi and so ATP  ADP + Pi
results in increased S (+ΔS)
– the ratio of [ATP]/[ADP] is high (far from equilibrium);
therefore ATP  ADP + Pi results in increased S (+ΔS)
– the negative charges of the γ and β phosphates repel each
other; therefore breaking the γ-β covalent bond and forming
more stable products results in negative ΔH (–ΔH)
– resonance stabilization of ADP and Pi
– stabilization by greater hydration of ADP + Pi vs ATP
• therefore, for ATP  ADP + Pi: –ΔH – (+ΔS) = – ΔG
Three reasons why ADP + Pi is more stable than ATP – (1)

• greater repulsion by the negatively charged phosphates of

ATP

γ β α
β α

http://www.asu.edu/courses/chm233/notes/halides/halidesRL2/atp.html
Three reasons why ADP + Pi is more stable than ATP – (2)

• greater hydration (solvation) of the negatively charged

phosphates of ADP + Pi by H2O

γ β α

http://www.asu.edu/courses/chm233/notes/halides/halidesRL2/atp.html
Three reasons why ADP + Pi is more stable than ATP – (3)
• ADP + Pi are more stable since both the terminal (β)
phosphate of ADP and the Pi can form stabilizing resonance
structures

Pi ADP

β α
+
resonance
structures

+
 A clarification
• The bond between the gamma and beta phosphates
of ATP is often referred to as a “high energy bond”
• This is misleading and confusing because it may
suggest that the bond is very strong.
• It is not! In fact, the bond is only intermediate in
strength.
• However, the hydrolysis of this bond leads to a large
release in Gibbs’ free energy (large –ΔG; highly
exergonic; spontaneous)
 Other fates for the γ phosphate
• sometimes ATP is simply hydrolyzed to ADP +
Pi
• other times, instead of the γ phosphate being
released as Pi, it used to phosphorylate a
substrate
• enzymes which make use of ATP (or other
NTPs) to phosphorylate a substrate are known
as kinases
How does the cell couple the hydrolysis of
ATP to non-spontaneous reactions?
• remember our example of hydroelectric
power: we have to put the turbines in the
path of the water in order to couple the
power of the water current to the rotation of
the turbines
• so how does the cell put a non-spontaneous
reaction “in the path” of ATP hydrolysis?
 Example of reaction (energy) coupling
• glycolysis is the process by which glucose is “burned”
for energy
• the first step in glycolysis is the phosphorylation of
glucose by the enzyme hexokinase to create glucose-
6-phosphate
• because this is non-spontaneous (+ΔG) it is coupled
to the hydrolysis of ATP (large –ΔG)
 Example (cont’d)
• ATP  ADP has a ΔG of –30.5 kJ/mol
• glucose  glucose-6-P has a ΔG of 13.8 kJ/mol
• therefore, the ΔG of the coupled reaction
glucose + ATP  glucose-6-P + ADP + Pi
= ΔGATPADP + ΔGglucoseglucose-6-P
= –30.5 kJ/mol + 13.8 kJ/mol = –16.7 kJ/mol
• therefore, the net ΔG of the coupled reaction is
still negative and so proceeds
 Enzymes are needed….
• to couple the exergonic and endergonic
reactions
• to increase the speed of the reaction
(spontaneous does not mean fast)
• enzymes couple the large –ΔG of ATP
hydrolysis to the smaller +ΔG of non-
spontaneous reactions
 Hexokinase (hexose kinase)
active site of the enzyme

ATP

nucleophilic
attack
..

glucose Without the enzyme, the

challenges are…
1. the reactants have to find
The enzyme acts to…
each other
1. bring the reactants into
2. the lone pair has to overcome
close proximity
the repulsion of the negatively
2. shield the negative charges
charged phosphate
on ATP
3. the ATP must not react with
3. exclude H2O
water first

http://watcut.uwaterloo.ca/webnotes/Metabolism/Glycolysis.html
Metabolism: Digestive system (Extracellular Metabolism)

LO28
 Note
• in revising LO28 for the final exam, it will be
suffcient to focus on the following slides
Monoglycerides
This would be true of a relatively healthy diet.
However, the food industry has taken to using
fructose as a sweetener. If you consume a lot
of processed sweet “foods”, such as soft
drinks, you are ingesting a lot of fructorse.
 Good to know this.

Not for
memorization.