Lecture 2 Unit Thermodynamics Chapter 1 Learning objectives:

Thermodynamics First Law

The First Law of Thermodynamics Energy (U) is conserved it can be neither created nor destroyed Most biological processes take place under constant pressure (P) and variable volume (V) The Enthalpy (H) of a process is defined as follows: H = U + PV H = U + PV (under constant pressure, the volume will change like the expansion of a gas) The volume changes in biological processes are practically negligible so H U
2

Thermodynamics Second Law

The Second Law of Thermodynamics Spontaneous processes are characterized by the conversion of order to disorder A process is spontaneous if it can occur without the input of additional energy from the outside of the system Entropy (S) is the measure of the degree of disorder in a system

In the system to the right, the first system has higher order than the second. The second is more disordered. The entropy increases on going from the first to the second system. The change in entropy is measured by: S = H/T (T=temperature)
3

Gibbs Free Energy (G)

The Free Energy (G) change of a spontaneous process is negative Free energy is defined as follows: G = H TS Normally, we are interested in the change in free energy so the following equation is more useful: G = H TS For a spontaneous process, G < 0. If the G is < 0, the process is called exergonic If the G is > 0, the process is called endergonic If the G is = 0, the process is called equilibrium
4

S

H

G = H - TS All favorable at all temperatures spontaneous Enthalpy favored. Spontaneous at temperatures below T = H S Entropy driven, enthalpy opposed. Spontaneous at Temperatures above T = H S Non-spontaneous
5

+ -

Equilibrium Constants
Relationships between concentration and free energy G = -RT ln Keq, where G0 is the free energy change in the standard state, R is the gas constant 8.3145 J/Kmol

aA + bB cC + dD
c [ D ]d [ ] C G = G 0 + RT ln [ A]a [ B]b

At equilibrium, G=0 so G = -RT ln Keq

d D [C ]c [ ] eq eq a [ B ]b [ A]eq eq

K eq =

=e

G 0 / RT
6

Keq can vary from 106 to 10-6 or more!!!

Go is a method to calculate two reactions whose Keqs are different

However
The initial products and reactants maybe far from their equilibrium concentrations

so

[C] [D] a b [A] [B]

Must be used

Each step of a biochemical process is not required to be exergonic. As long as the overall pathway is exergonic, it will operate in a forward manner.

Thus, the free energy of ATP hydrolysis, a highly exergonic reaction, is harnessed to drive many otherwise endergonic biological processes to completion!!
8

Standard state conventions in biochemistry

The concentration of pure water is assigned a value of 1 even though it is really 55.5M (M = Molar). Therefore, the terms for the concentration of water, [H2O], in equilibrium expressions can be ignored. The standard pH is 7.0 Temperature is 25oC Pressure is 1 atm (atmosphere) Standard concentration is 1M

Questions: A. True or False? 1. Free energy change is a measure of the rate of reaction. 2. Free energy change is a measure of the maximum amount of work available from a reaction. 3. Free energy change is a constant for a reaction under any conditions. 4. Free energy change is related to the equilibrium constant for a specific reaction. 5. Free energy change is equal to zero at equilibrium. 6. A spontaneous process always happens very quickly. 7. A spontaneous process can occur with a large decrease in entropy.
10

B. Consider the following reaction: Glucose-1-phosphate glucose-6-phosphate G = -1.7 kcal/mole. What is the equilibrium constant for this reaction at pH 7 and 25C?

C. Consider the reaction with H = 10 kJ and S = 45 JK-1. Is the reaction spontaneous (1) 10C, (2) at 90C ?

11

Chapter 2
Water Physical properties of water
Structure of water Water as a solvent Hydrophobic effect Osmosis and diffusion

Chemical properties of water

Ionization of water Acid-base chemistry Buffers

12