L3 - Energy Considerations Flashcards
State the first law of thermodynamics:
Energy cannot be created or destroyed but can be transformed from one form to another.
Define: the study of thermodynamics
It is the study of energy transformations.
Forms of energy in reaction: Bond energy
Mexo and Bendo Making bonds releases energy and breaking bonds requires energy. The stronger the bond, the more energy released/required. This is known as bond energy.
Bond energy of C-H, C-C, C=C, C=O, Hydrogen bonds and Van der Waals Interactions.
C-H –> 412 C-C –> 348 C=C –> 610 C=O –> 740 Hydrogen bonds –> 12-30 Van der Waals Interactions –> 0.4-4
Define: Enthalpy change ΔH
Sum of energy that is used to break and make bonds.
Define: Exothermic
ΔH-ve Heat lost to surroundings Reaction more likely to occur. Oxidation of glucose has ΔH of -2813.
Define: Endothermic
ΔH+ve Heat taken from surroundings to molecule. Some reactions do occur but not all.
State the second law of thermodynamics:
All processes must increase the entropy of the universe. These reactions are more favourable +ve ΔS.
Cells and thermodynamics: How do they increase entropy of universe?
Cell maintains organisation. By making large macromolecules, you decrease in entropy (2 to 1). This decreases entropy inside cell but increase entropy of universe by:
- Releasing heat into environment
- Releasing other small molecules such as CO2 into environment.
Define: Gibbs free energy
The useful energy available for a reaction. Overall energy from breaking and making bonds.
Gibbs equation:
ΔG=ΔH-TΔS
T is temp in kelvin.
S has kJK-1mol-1
ΔG and ΔH is kJmol-1
Define: Exergonic
ΔG -ve and reaction can occur spontaneously. Releases energy.
Define: Endergonic
ΔG +ve and reaction cannot occur spontaneously. requires energy.
Explain the relationship between ΔG of a reaction and direction of the reaction.
ΔG doesn’t tell us about the rate of a reaction. Large -ve value means that it could take many years for reaction to occur. (due to high Ea) Usually enzymes are used to lower Ea allowing reaction to occur.
ΔG and Equilibrium:
At equilibrium, ΔG=0. Reactant and product made is constant. For example, Y to X. Formation of X is favoured. ΔG = -ve Formation of Y is not. ΔG = +ve ΔG and direction of reaction depends on conc of reactants and products.
Standard States
ΔG°’ is the free energy change of a reaction under standard conditions of: 1M conc of reactants and products. 25°C (298K) pH=7 (biological systems) ΔG° has pH = 0 for chemists.
Factors that affect direction of a reaction:
- Volume of conc
- Ratio of conc of products and reactants.
More reactants then reaction goes to right. More products then reaction goes to left.
ΔG also determines the direction of the reaction.
ΔG and ΔG°’ Equation:
ΔG = ΔG°’ + RTlnKa
At equilibrium ΔG=0 so: ΔG°’ = -RTlnKa
R=8.314JK-1mol-1 → 0.008314kJK-1mol-1
T in kelvin.
ΔG°’ in kJmol-1
Ka in kJmol-1
As ΔG°’ increases (more exergonic/negative) then more product is formed so Ka is higher.
Ka = Products/reactants
Energetically unfavourable reactions
They can be coupled with favourable reactions, usually hydrolysis of ATP.
Glutamate+NH4+ + ATP → Glutamine+ADP+Pi Glutamate + NH4(+) = Glutamine + H2O
ΔG°’ = +15 kJmol-1
H2O + ATP = ADP + Pi
ΔG°’ = -30 kJmol-1
Use enzymes to couple them.