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Thermodynamics PDF

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175 views20 pages

Thermodynamics PDF

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Valine Cysteine Methionine
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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)

© Pearson Education Ltd 2015.


Copying permitted for
purchasing institution only.
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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