GIBBS FREE ENERGY

JOHN M. ROBINSON MD, PHD

1. Background Regarding the transformation of matter, we are concerned about two things: (i) can it happen? and (ii) how fast? Equilibrium thermodynamics (sometimes called thermodynamics) deals with the rst question. Non-equilibrium thermodynamics (usually called kinetics) deals with the second question. Here, we are interested in the rst question. 2. First Law of Thermodynamics The rst law of thermodynamics states that the change in internal energy U equals heat dq given to the system minus the dierent kinds of work dwi done by the system, dU = dq
i

dwi .

Work comes in two avors: non-mechanical work and mechanical work, dwmech = P dV , where P is pressure and V is volume. There are many kinds of non-mechanical work; examples are chemical work and electrical work. Here, we consider chemical work of multiple species j = 1, 2, . . .. Dierent species might be dierent molecules or the same molecule in dierent phases (like gas, liquid, solid) or the same molecule in dierent structural states (like the active and inactive conformations of an enzyme). The chemical work of species j is dwchem,j = j dnj , where j is the chemical potential (dened below) of species j , and nj are the number of molecules of species j ; other kinds of non-mechanical work are denoted with an elipsis (. . .). Combining, we obtain dU = dq P dV +
j

j dnj + . . .

as a statement of the rst law of thermodynamics. We could get fancy and collect the chemical potentials of all species into the tuple = (1 , 2 , . . .) and collect the number of molecules of all species into the tuple n = (n1 , n2 , . . .). Now, the sum is the dot product, j j dnj = dn. In the revised notation, the rst law of thermodynamics is (1) dU = dq P dV + dn + . . . . dU = dq P dV.
Date : December 12, 2010.
1

Considering only mechanical work,

JOHN M. ROBINSON MD, PHD

When the transformation happens at constant volume (dV = 0, so there is no mechanical work, P dV = 0) and there are is no non-mechanical work, the change in internal energy dU is the heat gained by the system (dU )V = (dq )V . 3. Enthalpy We have just seen that when volume is constant, the change in internal energy equals heat. Trouble is that the systems that we will be studying are at constant pressure, so we want an simple relationship between something and heat when pressure is constant. Dene a new state function called enthalpy, H = U + P V . Dierential enthalpy is dH = dU + P dV + V dP. Substituting Eq. 1, dH = dq + V dP + dn + . . . . When the transformation happens at constant pressure (dP = 0) and there are is no non-mechanical work, the change in enthalpy dH is the heat gained by the system (2) (dH )P = (dq )P .

So, when we want do describe heat transfer in a system whose volume is xed, we use dU . When we want do describe heat transfer in a system whose pressure is xed, we use dH . Pretty simple! 4. Second Law of Thermodynamics Think of an ideal gas as a bunch of really small hard spheres. The spheres dont sense one another except when they attempt to occupy the same place, in which case they collide and bounce o each other. For those of you that are interested, the potential that describes the collision is zero outside of the sphere and innite in the sphere. So, force, being the gradient of the potential is zero until the gas molecules collide, then it is innite. As you would expect, momentum is conserved in the collision. The experimental observation is that an ideal gas will spontaneously sample all of the dierent arrangements that are available to it. There is, evidently, something pushing the gas molecules to explore the possibilities. What is really doing the pushing are all those collisions. The rst law of thermodynamics is powerless to describe this push. Why? Because pushes involve force, and force appeals to time, the rst law of thermodynamics doesnt know about time. Since we describe things in terms of energy, we need to nd a way to quantify this push in terms of energy. Entropy allows us to do this. 4.1. Statistical denition of entropy. The considerations above can be described in the number of ways that the system can congure itself. Need to work on this.! Boltzman entropy is S = k ln W.

GIBBS FREE ENERGY

4.2. Thermodynamic denition of entropy. Entropy is dened somewhat mysteriously as (3) dS dq/T.

The second law of thermodynamics is a statement about the heat of the universe: (4) dquniv 0.

Second law of thermodynamics says that in any transformation of the universe, the universe will either heat up (dquniv > 0) or it wont heat up (dquniv = 0). When dquniv > 0, the transformation is spontaneous. When dquniv = 0, the transformation is reversible. Eq. 4 says that the universe will never cool down! Think about this for a second. The universe cant exchange energy with anything (it is an isolated system) so the internal energy of the universe cant change (dUuniv = 0). So, if the universe heats up then work is being done to make heat, dw dq . In terms of entropy, the second law of thermodynamics is T Suniv 0. When T Suniv > 0, the transformation of the universe is spontaneous. When T Suniv = 0, the transformation of the universe is reversible. We can divide the universe into a region of interest (called the system) and everything else (called the surroundings). State functions, like internal energy and entropy, separate. So, for instance, Uuniv = Usys + Usurr and Suniv = Ssys + Ssurr . We allow the system to exchange heat with the surroundings. Heat from system is transferred to the surroundings dqsys = dqsurr . We are thinking about systems and surroundings that are at constant pressure, which means that we will be using dH . Eq. 2 tells us that dqsys = dHsys . So, heat transfer between the system and the surroundings can be expressed as (5) T dSsurr = dHsys .

The second law of thermodynamics can be transformed into a statement about the energy of the system, T dSsys dHsys 0. This motivates our dening a new state function, the Gibbs free energy, G = H T S. The dierential Gibbs free energy is dG = dH T dS SdT . For a system at constant temperature (due to the surroundings giving and taking heat to keep the temperature of the system constant), dG = dH T dS (c.f. Eq. 5). Thus, when our focus is a system (not the whole universe) that is under constant temperature and pressure the second law of thermodynamics is dGsys 0 .

JOHN M. ROBINSON MD, PHD

From now on, we will focus on the system, so I will drop the subscript sys; just remember that from now on, everything refers to the system. The system is at equilibrium when dG = 0. A transformation of the system will spontaneously occur when dG < 0. 5. Focus on the system For a sysem consisting of a single chemical species and, as above, considering only two forms of work (mechanical work and chemical work), the Gibbs free energy is a state function dened by G = U T S + P V. The dierential of Gibbs free energy is dG = dU T dS SdT + P dV + V dP = (T dS P dV + dn + . . .) T dS SdT + P dV + V dP, where we have used Eq. 1 and Eq. 3. Canceling terms, we obtain (6) dG = SdT + V dP + dn + . . .

We regard the Gibbs free energy as a function of three (natural) variables: temperature, pressure, and the number of molecules, G = G(T, P, n). For systems that operate at constant temperature (dT = 0) and constant pressure (dP = 0), (dG)T,P = dn + . . . . Thus, the dierential Gibbs free energy is the energy that is available to do non-mechanical work, like chemical work, under constant pressure and constant temperature. This is why it is called free energy. 6. Chemical Equilibria Imagine that we had a chamber of an ideal gas. We ask, what is the change in Gibbs free energy associated with the perturbation of this gas either by a change in pressure. To examine the eect of a change in pressure, we couple the chamber of ideal gas to a movable piston. We now reversibly adjust the pressure on the piston from P P .
G P P

dG =
G P

V dP =
P

nRT dP. P

Carrying out the integration, we obtain G = G + nRT ln(P/P ), where G is some reference free energy. Now, since G is a state function, we can express it as a total dierential of its natural variables G G G dT + dP + dni dG = T P ni
i

GIBBS FREE ENERGY

Comparing with Eq. 6, we can make the following associations G T G P and most importantly, G ni So, = RT ln(P/P ). For liquids we make the approximation that the concentration (X ) is proportional to its partial pressure. So for a liquid, = RT ln((X )/(X )), where (X ) is the standard state concentration of the molecule. Dening or = RT ln(X ), we obtain the desired expression for the chemical potential of a molecule (7) = + RT ln(X ) . 7. Chemical Work Consider the reaction B B, A A where i is the stoichiometry of the chemical species i. The Gibbs free energy depends on the chemical potential of A (A ) and the chemical potential of B (B ), dG = SdT + V dP + A dnA + B dnB . It is convenient to dene the variable as a measure of reaction progress, and express the change in molar concentrations of A and B in terms of changes in : dnA = A d and dnB = b d . We obtain dG = SdT + V dP + (A A + b B )d. At constant temperature and pressure, (dG)T,P = (A A + b B )d. At equilibrium, dG = 0. The condition for chemical equilibrium is A A + b B = 0. Inserting Eq. 7,
0 = A ( A + RT ln(A)) + B (B + RT ln(B )), which can be rewritten as A B 0 = A + B A RT ln(A) B + RT ln(B ) .

= S ;
P,{ni }

=V;
T,{ni }

= i ;
T,P,{nj =i }

JOHN M. ROBINSON MD, PHD

After rearranging, = RT ln where

[B ]B [A]A

= B B A A . Here, the concentration of A is denoted (A), and the concentration of A at equilibrium is denoted [A]. We dene a molar Gibbs free energy G = G/ , the change G = dG/d is

(8)

(G)T,P = + RT ln

(B )B (A)A

Eq. 8 is easily generalized to reactions that involve more species. Eq. 8 is important since it treats systems, like a living cell, that are not in equilibrium. 7.1. Example. Consider the hydrolysis of ATP ADP + Pi AT P Knowing the standard change of chemical potential and the intracellular concentrations of ATP, ADP, and Pi , we can calculate the maximum work Wmax that can be done by the hydrolysis one mole (n = 1) of ATP, Wmax = + RT ln (ADP )(Pi ) (AT P ) .

When a cell dies, the ATP battery runs down: (ADP )(Pi )/(AT P ) = [ADP ][Pi ]/[AT P ]. Eq. 8 tells us that (G)T,P = 0, as we expect. Can a dead cell do work? No, Wmax = 0.