Thermodynamics PDF

Thermodynamics applied to
biochemistry
A→B
• What are the energetics involved in this process?
• Will this process occur spontaneously?
Thermodynamics!
The first law of thermodynamics:
The first law of thermodynamics: the total energy of a system
and its surrounding is constant.
• For a certain process within a system, the change in energy is the
sum of absorbed heat and work done by the system
ΔU = Ufinal – Uinitial = q - w w
H = U + PV At constant P: ΔH = ΔU + PΔV
• Most biological processes occur under constant pressure (P) and
constant volume (V), therefore the enthalpy change (ΔH) equals heat
change (q)
ΔH = q
q is the heat exchange between the system and the environment,
Positive: absorbed heat from the environment
Negative: release heat to the environment
The second law of thermodynamics
The total entropy of a system and its surroundings

always increases in a spontaneous process.
Δstotal > 0
Entropy is a measure of disorder in a system
• S = kBlnW
kB = Boltzmann s constant
W: number of energetically equivalent ways to arrange
components of a system.
Free energy: the second law in open systems
§ Living systems are not isolated systems, so we need to state the second
law of thermodynamics in terms that are relevant to open systems
ΔStotal = ΔSsurrounding + ΔSsystem
ΔSsurrounding = ΔHsurrounding/T = -ΔHsystem/T
ΔStotal = ΔSsystem - ΔHsystem/T

Multiple (–T) on both sides
-TΔStotal = ΔHsystem - TΔSsystem

• The term TΔS has the unit of energy and is referred to as
the Gibbs free energy.
ΔG = -TΔStotal = ΔHsystem - TΔSsystem

Free Energy
The Gibbs free energy is essentially an accounting tool to
keep track of entropy changes of both the system and the
surrounding.
ΔG = -TΔStotal = ΔHsystem - TΔSsystem
• Free energy (G, J. mol-1) has two components: enthalpy (H, J.

mol-1) and entropy (S, J. K-1. mol-1).
• H is a measure of the heat of the system.
• S is a measure of disorder of the system.
• Free energy is a state function, therefore the ∆G of a reaction
is independent of the path (or molecular mechanism) of the
transformation.
ΔG = ΔH - TΔS
Free energy change of a process
A B ΔG = -TΔStotal
ΔG dictates the directionality of a process
• If ΔG = 0, reaction is at equilibrium
• If ΔG < 0, reaction occur spontaneously: exergonic
• If ΔG > 0, reaction proceeds in reverse: endergonic
• ∆G provides no information about the rate of a
reaction. A negative ∆G can occur spontaneously,
but it does not signify the rate of the reaction.
ΔG = ΔH - TΔS
Example of the interplay of enthalpy
and entropy
Is it energetically favorable for ice to melt at 263 K
(-10 ˚C), where ΔH is +5630 J/mol and ΔS is
+20.6 J/K•mol?
ΔG is positive and the melting of ice at at 263 K is

unfavorable
Is it energetically favorable for ice to melt at 283 K
(+10 ˚C), where ΔH is +6770 J/mol and ΔS is
+24.7 J/K•mol?
ΔG is negative and the melting of ice at at 283 K

is favorable
Contributions of enthalpy and entropy
to exergonic processes
Free energy, chemical reactions, and
equilibrium
§ Consider the general reaction
§ The equilibrium constant, K, can be written as
§ And Q, symbolizes the mass action expression
At equilibrium, what is the relationship between Q and K?

ΔG
For a reaction at equilibrium, ΔG = 0
Or
and this can be rearranged to

Free energy, chemical reactions, and
equilibrium
§ The free energy change of a chemical reaction (ΔG) depends on:

§ the standard free energy change (ΔG˚), which can be determined
from K
§ the concentrations of the reactants and products (described by RT
ln Q)
§ When the system is at equilibrium Q = K

ΔG = -RTlnK + RTlnQ = RTln(Q/K)
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Exercise 1
• If this reaction is set up in a test tube, at equilibrium, the

concentration of G6P is 2mM, what is the concentration of F6P?
• Inside the cell, at a given moment G6P and F6P concentrations

inside the cell are 4 mM and 1 mM, what is the favored direction
of the reaction?
To answer these two questions, we first need to calculate the equilibrium
constant from ΔG0
• If this reaction is set up in a test tube, at equilibrium, the concentration of G6P is 2mM, what is the
concentration of F6P
[F6P]/[G6P] = 0.504
[F6P] = [G6P](0.504) = 2 mM x 0.504 = 1.08 mM
• side the cell, at a given moment G6P and F6P concentrations inside the cell are 4 mM
and 1 mM, what is the favored direction of the reaction?
Q = [F6P]/[G6P] = 1 mM/4 mM = 0.25

ΔG = -RTlnK + RTlnQ = RTln(Q/K) = RTln(0.25/0.50) < 0
Therefore, the favored direction is G6P conversion to F6P

• The concentrations of metabolites of a certain
process inside a living cell is usually not at
equilibrium!
• In the cell, steady-state concentrations (homeostatic

condition) are maintained far from equilibrium
values, i.e., the homoeostatic condition maintains Q
far from K such that ΔG ≠ 0
• Energy is required to maintain homeostasis!

How is life thermodynamically possible
Free energy in a coupled reaction
• Cells couple unfavorable

processes with favorable
ones so that the net
change in ∆G is negative.
unfavorable A→B ΔG = 15 kJ .mol-1

favorable B → C ΔG = -20 kJ. mol-1
A + B → B + C ΔG = -5 kJ .mol-1
How is life thermodynamically possible
Coupling is used to drive unfavorable chemical reactions, pump metabolites

across membranes against a concentration gradient, transmit nerve
impulses, contract muscles, etc.
Standard States
• To compare thermodynamic parameters of different reactions, these
parameters must be measured or calculated under a standard state .
• By definition, a standard state is:

T = 298 K (25 C); p = 1 atm; Concentrations of all reactants = 1.0 M
• Parameters measured or calculated under standard state condition are

denoted by a superscript o sign: ΔH , ΔS , ΔG , etc
• In biochemical reactions, for the standard state, by convention

• Water activity is assigned a value of 1.
• pH = 7
• Denoted by: ΔGo , ΔH , ΔS ’

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Thermodynamics applied to

The total entropy of a system and its surroundings

ΔSsurrounding = ΔHsurrounding/T = -ΔHsystem/T

ΔStotal = ΔSsystem - ΔHsystem/T

-TΔStotal = ΔHsystem - TΔSsystem

ΔG = -TΔStotal = ΔHsystem - TΔSsystem

ΔG = -TΔStotal = ΔHsystem - TΔSsystem

• Free energy (G, J. mol-1) has two components: enthalpy (H, J.

ΔG is positive and the melting of ice at at 263 K is

ΔG is negative and the melting of ice at at 283 K

§ The equilibrium constant, K, can be written as

§ And Q, symbolizes the mass action expression

At equilibrium, what is the relationship between Q and K?

For a reaction at equilibrium, ΔG = 0

and this can be rearranged to

§ The free energy change of a chemical reaction (ΔG) depends on:

§ When the system is at equilibrium Q = K

© Pearson Education Ltd 2015.

• If this reaction is set up in a test tube, at equilibrium, the

• Inside the cell, at a given moment G6P and F6P concentrations

[F6P] = [G6P](0.504) = 2 mM x 0.504 = 1.08 mM

Q = [F6P]/[G6P] = 1 mM/4 mM = 0.25

Therefore, the favored direction is G6P conversion to F6P

• In the cell, steady-state concentrations (homeostatic

• Energy is required to maintain homeostasis!

• Cells couple unfavorable

unfavorable A→B ΔG = 15 kJ .mol-1

Coupling is used to drive unfavorable chemical reactions, pump metabolites

• By definition, a standard state is:

• Parameters measured or calculated under standard state condition are

• In biochemical reactions, for the standard state, by convention

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