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Garrett2e Chapter03
Garrett2e Chapter03
Chapter 3
Thermodynamics of Biological
Systems
to accompany
Biochemistry, 2/e
by
Reginald Garrett and Charles Grisham
All rights reserved. Requests for permission to make copies of any part of the work
should be mailed to: Permissions Department, Harcourt Brace & Company, 6277
Sea Harbor Drive, Orlando, Florida 32887-6777
Copyright © 1999 by Harcourt Brace & Company
Biochemistry 2/e - Garrett & Grisham
Outline
• Basic Thermodynamic Concepts
• Physical Significance of
Thermodynamic Properties
• pH and the Standard State
• The Effect of Concentration
• Coupled Processes
• High-Energy Biomolecules
Basic Concepts
• The system: the portion of the universe
with which we are concerned
• The surroundings: everything else
• Isolated system cannot exchange matter
or energy
• Closed system can exchange energy
• Open system can exchange either or
both
Enthalpy
A better function for constant pressure
• H = E + PV
• If P is constant, H = q
• H is the heat absorbed at constant P
• Volume is approx. constant for
biochemical reactions (in solution)
• So H is approx. same as E
Entropy
• A measure of disorder
• An ordered state is low entropy
• A disordered state is high entropy
• dSreversible = dq/T
Free Energy
• Hypothetical quantity - allows chemists
to asses whether reactions will occur
• G = H - TS
• For any process at constant P and T:
G = H - TS
• If G = 0, reaction is at equilibrium
• If G < 0, reaction proceeds as written
G versus Go’
• How can we calculate the free energy
change for rxns not at standard state?
• Consider a reaction: A + B C + D
• Then:
G = Go’ + RT ln ([C][D]/[A][B])
Energy Transfer
A Crucial Biological Need
• Energy acquired from sunlight or food
must be used to drive endergonic
(energy-requiring) processes in the
organism
• Two classes of biomolecules do this:
– Reduced coenzymes (NADH, FADH2)
– High-energy phosphate compounds - free
energy of hydrolysis larger than -25 kJ/mol)
High-Energy Biomolecules
Study Table 3.3!
• Note what's high - PEP and 1,3-BPG
• Note what's low - sugar phosphates,
etc.
• Note what's in between - ATP!
• Note difference (Figure 3.8) between
overall free energy change - noted in
Table 3.3 - and the energy of activation
for phosphoryl-group transfer!
ATP
An Intermediate Energy Shuttle Device
• PEP and 1,3-BPG are created in the
course of glucose breakdown
• Their energy (and phosphates) are
transferred to ADP to form ATP
• But ATP is only a transient energy
carrier - it quickly passes its energy to a
host of energy-requiring processes
Copyright © 1999 by Harcourt Brace & Company
Biochemistry 2/e - Garrett & Grisham
Phosphoric-Carboxylic
Anhydrides
• These mixed anhydrides - also called
acyl phosphates - are very energy-rich
• Acetyl-phosphate: G°´ = -43.3 kJ/mol
• 1,3-BPG: G°´ = -49.6 kJ/mol
• Bond strain, electrostatics, and
resonance are responsible
Enol Phosphates
• Phosphoenolpyruvate (PEP) has the
largest free energy of hydrolysis of any
biomolecule
• Formed by dehydration of 2-phospho-
glycerate
• Hydrolysis of PEP yields the enol form
of pyruvate - and tautomerization to the
keto form is very favorable
Copyright © 1999 by Harcourt Brace & Company
Biochemistry 2/e - Garrett & Grisham