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Biological systems are open Develop our understanding of the utility of G Introduce thermodynamic equilibrium (helps us to determine G°´) Effect of T on thermodynamic equilibrium

Biological systems are open

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Develop our understanding of the utility of  G Introduce thermodynamic equilibrium (helps us to determine  G°´) Effect of T on thermodynamic equilibrium. Biological systems are open. - PowerPoint PPT Presentation

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Page 1: Biological systems are open

Biological systems are open

• Develop our understanding of the utility of G

• Introduce thermodynamic equilibrium (helps us to determine G°´)

• Effect of T on thermodynamic equilibrium

• Develop our understanding of the utility of G

• Introduce thermodynamic equilibrium (helps us to determine G°´)

• Effect of T on thermodynamic equilibrium

Page 2: Biological systems are open
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)*( PdVdwdw revrev

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Thermodynamics of open systems (reaction mixes)

We need to handle systems that contain more than one component, the concentrations of which can vary (e.g. a solution containing a number of dissolved reactants). These are called open systems.

Consider: A + B <===> C + D

There are four solutes (reactants or products) and the concentrations of A, B, C and D are affected by this and other reactions. How do we calculate G for this reaction?

Page 9: Biological systems are open

Thermodynamics of open systems (reaction mixes)

For one component (A): GA = GA°´ + nART.ln[A]

And for 1 mole of A:

where the units are free energy per mole (J mol-1). This quantity is also known as the chemical potential (µA) and we write:

µA = µA°´ + RT.ln[A]

Previously we had for the general case: dG = Vdp - SdT

For open, multicomponent systems, we write:

dG = Vdp - SdT + i µidni

G A G Ao 'RT ln[A]

Page 10: Biological systems are open

Thermodynamics of open systems (reaction mixes)

In biological systems (constant p and T):

dG = i µidni or G = i µini

We can now calculate G for a specific reaction:

aA + bB <===> cC + dD

where the reactants are A and B, the products are C and D. a, b, c and d represent the number of moles of each that participate in the reaction. For this reaction:

G = Gproducts - Greactants

= (cµc + dµd) - (aµa + bµb)

Page 11: Biological systems are open

Thermodynamics of open systems (reaction mixes)

But µA = µA°´ + RT.ln[A] etc. so:

G = [(cµc°´ + dµd°´) - (aµa°´ + bµb°´) + RTln([C]c[D]d/[A]a[B]b)

which we express as:

G = G°´ + RTln([C]c[D]d/[A]a[B]b) (Joules)

To find the free energy change per mole, note that a, b, c and d will reflect the stoichiometry of the reaction (the numbers of each type of molecule involved in a single reaction). For example, a single reaction might involve the following numbers of molecules:

2A + 1B <----> 1C + 2D

which is the same as: A + A + B <----> C + D + D

Page 12: Biological systems are open

Thermodynamics of open systems (reaction mixes)

We now have an equation which allows us to calculate G in practice:

(J mol-1)

a, b, c and d are the stoichiometric coefficients.

G°´ is the standard free energy change per mole.

G Go RT lncC dD aA bB

Standard free energy change per mole is the free energy change that occurs when reactants at 1 M are completely converted to products at 1 M at standard p, T and pH.

Page 13: Biological systems are open

Thermodynamic equilibrium

We calculate G so that we can determine the spontaneous direction of a reaction (favourable or unfavourable). To do that we must determine:

G°´• the concentration of each component • the stoichiometry of the reaction.

We need G < 0 for a favourable forward reaction. We can drive the reaction forward either by:

• increasing [A] and/or [B]• decreasing [C] and/or [D]

Living cells can (sometimes) control reactant/product concentrations to ensure that G < 0 for desired reactions.

G G o 'RT lncC dD aA bB

Page 14: Biological systems are open

Thermodynamic equilibrium

In many cases there is a dynamic steady state: new reactants are made and products consumed in other reactions in order to keep concentrations steady. So G holds constant and, if it is negative, the reaction keeps going.

If the cell dies, the reaction will reach thermodynamic equilibrium and come to a halt. Let’s see what happens:

We have:

If G < 0 at time zero and the system is isolated, then G becomes less negative as the concentrations of C and D build up (and those of A and B decline). Eventually equilibrium is reached when G =0.

G G o 'RT lnC c

D d

A aB b

Page 15: Biological systems are open

Thermodynamic equilibrium

At equilibrium,

and define the equilibrium constant K:

This constant depends on the chemical natures of the reactants and products. We measure G°´ by measuring the concentrations of A, B, C and D once the reaction has reached equilibrium.

G o ' RT lnC c

D d

A aB b

eq

K C c

D d

A aB b

eq

Page 16: Biological systems are open

Thermodynamic equilibrium

Note: if G°´ < 0, then ([C][D])eq > ([A][B])eq (for a=b=c=d=1)

if G°´ > 0, then ([C][D])eq < ([A][B])eq

Thus, G°´ determines whether the reactants or products predominate at equilibrium. T

Thermodynamic equilibrium is not a static state (conversion of A and B to C and D and back again keeps going but there is no net change in their concentrations).

Page 17: Biological systems are open

The effect of temperature

We can write: G°´ = -RTlnK = H°´ - TS°´

Thus, ln K Go'

RT

Ho'

R

1

T

So'

R

We can therefore plot lnK vs 1/T to determine H°´ and S°´, the standard enthalpy and entropy of the reaction respectively.

Such a plot is known as a Van’t Hoff plot. It will give a straight-line if H°´ is independent of T (usually true for narrow ranges of T).

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Summary

(1) The sign of G tells us the spontaneous direction of a reaction:

G < 0, forwardG > 0, reverseG = 0, equilibrium

(2) G°´, the standard free energy change for a reaction determines the relative concentrations of reactants and products that will be found at thermodynamic equilibrium.

(3) Neither quantity tells us about the rate of the reaction.

K G ' RTe C c

D d

A aB b

eq

See a textbook for more details on G and G°´ - we will see this later on at transition state theory

Page 19: Biological systems are open

References

1. Biological Physics. Energy, Information, Life Philip Nelson, (Freeman and Company, New York, 2004).

2. Principles of Physical Biochemistry, chapter 2, pp. 69-89 Kensal E. van Holde, W. Curtis Johnson and P. Shing Ho (Pretice Hall, Upper Saddle River, 1992).