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Chapter 4: Outline
Thermodynamics First Law Second Law Free Energy Standard free energy changes Coupled reactions Hydrophobic effect (revisited) Role of ATP
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4.1 Thermodynamics
The heat and energy transformations studied by thermodynamics take place in a system (defined by the investigator) connected to the surroundings (the rest of the universe). Closed system: energy exchanged between system and surroundings. Open system-matter and energy exchanged between system and surroundings.
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First Law-1
Energy is neither created nor destroyed. or DE = q+w DE is the change in the internal energy and is a state function, i. e. independent of path. q is heat and is not a state function. w is work and is not a state function.

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First Law-2
Biochemical systems function at constant pressure, volume, and temperature. H(enthalpy) = E + PV or DH = DE and DH = q (heat flow) The change in enthalpy for a reaction is calculated using the equation DHreactants = DHproducts DHreactants

-DH is exothermic

+DH is endothermic 4-9

First Law-3
Given the equation and the DHf values, calculate the DH for the reaction.

6 CO2 + 6 H2O C6H12O6 + 6 O2

C6H12O6 O2 kJ/mol -304.7 0 CO2 H2O kJ/mol -94.0 -68.4

[1*-304.7+6*0]-[6*-94.0+6*-68.4)]=+670 kJ Prod - Reactants

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Second Law
With a spontaneous reaction, the entropy of the universe increases. DSuniv = DSsystem + Dssurroundings In irreversible processes, entropy is a driving force.

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Bioenergetics
Each formation or breakdown of a biomolelcule involves an associated energy change. Thermodynamics is the field of chemistry that studies these energy changes. The goal of thermodynamics is to predict whether a reaction will occur spontaneously which, in a chemical sense, means it will continue without energy input once started.
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4.2 Gibbs Free Energy

Gibbs free energy change (DG) is the most useful thermodynamic function for predicting reaction spontaneity. The two other thermodynamic quantities that contribute to the value for DG: DH=enthalpy change (energy change measured at constant pressure) DS=entropy change (related to the state of disorder in a system)
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Gibbs Free Energy: 2

The three thermodynamic quantities are related by the following equation:

For biochemists, DG is usually measured at 25 oC, one atm for a gas, and at a concentration of 1 M for solutes except hydronium ion which is at pH 7. These conditions specify a standard DG o represented as DG .
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DG = DH -TDSsys

Gibbs Free Energy: 3

In a spontaneous reaction: free energy decreases, DG is negative energy is released by the reaction reaction is said to be exergonic In a nonspontaneous reaction: free energy increases, DG is positive energy is absorbed by the reaction reaction is said to be endergonic
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Examples, DG values
(From standard tables)
o DG ,kJ/mol

(kcal/mol)

Exergonic reaction: ATP + H2O ADP + Pi Endergonic reaction: glucose-6-phosphate to fructose-6-phosphate

-30.5 (-7.3)

+ 1.7 (+0.4)

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o DG and

Keq

For the reaction aA + bB = cC + dD

DG =
o DG

+ RT ln

c d [C] [D]

[A]a[B]b
At equilibrium, DG = 0 DGo = - RT ln Keq
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4.3 Bioenergetics and ATP

Hydrolysis of adenosine triphosphate (ATP) provides the free energy to drive most endergonic reactions. NH
2

O O O N O P O P O P O CH2 N O O O O H H ADP + Pi = -7.3 kcal/mol H H AMP + PPi = -7.7 kcal/mol OH OH

PPi 2 Pi = -8 kcal/mol

N N

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Coupled Reactions
Frequently in biochemistry two reactions are coupled or run as a pair. One reaction is endergonic but the second reaction is exergonic. The sum of the reactions (and the DG changes) is overall exergonic and consequently the reaction pair is overall spontaneous. This is shown on the next slide.

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Coupled Reactions: 2

o DG (kcal/mol)

1. glucose-6-P fructose-6-P + 0.4 2. fructose-6-P + ATP fructose-1,6-bisP + ADP - 3.4 3. glucose-6-P + ATP fructose-1,6-bisP + ADP - 3.0 The overall reaction 3 (sum of 1+2) is o o exergonic. Sum of DG 1 + DG 2 is DGo 3 or 3.0 kcal/mol. Overall reaction is spontaneous
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ATP
Drives several processes: Biosynthesis of biomolecules Active transport across membranes Mechanical work (e. g. muscle contraction) Can carry phosphoryl groups from higher-energy compounds to lowerenergy compounds.
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DG for ROPO3
o

2-

+ H2O
kcal/mol -3.3 -3.8 -7.7 -7.3 -10.3 -11.8 -14.8
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kJ/mol Glucose-6-P -13.8 Fructose-6-P -15.9 ATPAMP + PPi -32.3 ATPADP + Pi -30.5 P-creatine -43.1 Glycerate-1,3-bP -40.4 Phosphoenolpyruvate -61.9

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The End
Energy

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