Thermodynamics applied to

biochemistry

AB
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
U = Ufinal Uinitial = q - w w
H = U + PV At constant P: H = U + PV
Most biological processes occur under constant pressure (P) and
constant volume (V), therefore the enthalpy change (H) equals heat
change (q)
H = 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.

stotal > 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
Stotal = Ssurrounding + Ssystem

Ssurrounding = Hsurrounding/T = -Hsystem/T

Stotal = Ssystem - Hsystem/T

Multiple (T) on both sides

-TStotal = Hsystem - TSsystem

The term TS has the unit of energy and is referred to as
the Gibbs free energy.

G = -TStotal = Hsystem - TSsystem

 Free Energy
The Gibbs free energy is essentially an accounting tool to
keep track of entropy changes of both the system and the
surrounding.

G = -TStotal = Hsystem - TSsystem

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.
G = H - TS
 Free energy change of a process
A B G = -TStotal
G dictates the directionality of a process
If G = 0, reaction is at equilibrium
If G < 0, reaction occur spontaneously: exergonic
If G > 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.

G = H - TS
 Example of the interplay of enthalpy
and entropy
Is it energetically favorable for ice to melt at 263 K
(-10 C), where H is +5630 J/mol and S is
+20.6 J/Kmol?

G 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 H is +6770 J/mol and S is
+24.7 J/Kmol?

G 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?

 G

For a reaction at equilibrium, G = 0

Or

and this can be rearranged to

 Free energy, chemical reactions, and
equilibrium

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

the standard free energy change (G), 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

 G = -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 G0

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

G = -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 G 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 AB G = 15 kJ .mol-1
favorable B C G = -20 kJ. mol-1
A + B B + C G = -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: H , S , G , etc

In biochemical reactions, for the standard state, by convention

Water activity is assigned a value of 1.
pH = 7
Denoted by: Go , H , S